Aqueous zinc-ion batteries are regarded as promising electrochemical energy-storage systems for various applications because of their high safety,low costs,and high capacities.However,dendrite formation and side react...Aqueous zinc-ion batteries are regarded as promising electrochemical energy-storage systems for various applications because of their high safety,low costs,and high capacities.However,dendrite formation and side reactions during zinc plating or stripping greatly reduce the capacity and cycle life of a battery and subsequently limit its practical application.To address these issues,we modified the surface of a zinc anode with a functional bilayer composed of zincophilic Cu and flexible polymer layers.The zincophilic Cu interfacial layer was prepared through CuSO_(4)solution pretreatment to serve as a nucleation site to facilitate uniform Zn deposition.Meanwhile,the polymer layer was coated onto the Cu interface layer to serve as a protective layer that would prevent side reactions between zinc and electrolytes.Benefiting from the synergistic effect of the zincophilic Cu and protective polymer layers,the symmetric battery exhibits an impressive cycle life,lasting over 2900 h at a current density of 1 m A·cm^(-2)with a capacity of 1 m A·h·cm^(-2).Moreover,a full battery paired with a vanadium oxide cathode achieves a remarkable capacity retention of 72%even after 500 cycles.展开更多
Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the sol...Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the solid-electrolyte interphase(SEI)during extended cycling use may result in dendrite growth,which can penetrate the separator and pose significant short-circuit risks.Forming a stable SEI is essential for the long-term operation of the batteries.Fluorine-rich SEI has garnered significant attention for its ability to effectively passivate electrodes,regulate lithium deposition,and inhibit electrolyte corrosion.Understanding the structural components and preparation methods of existing fluorinated SEI is crucial for optimizing lithium metal anode performance.This paper reviews the research on optimizing LiF passivation interfaces to protect lithium metal anodes.It focuses on four types of compositions in fluorinated SEI that work synergistically to enhance SEI performance.For instance,combining compounds with LiF can further enhance the mechanical strength and ionic conductivity of the SEI.Integrating metals with LiF significantly improves electrochemical performance at the SEI/anode interface,with a necessary focus on reducing electron tunneling risks.Additionally,incorporating polymers with LiF offers balanced improvements in interfacial toughness and ionic conductivity,though maintaining structural stability over long cycles remains a critical area for future research.Although alloys combined with LiF increase surface energy and lithium affinity,challenges such as dendrite growth and volume expansion persist.In summary,this paper emphasizes the crucial role of interfacial structures in LMBs and offers comprehensive guidance for future design and development efforts in battery technology.展开更多
Aqueous batteries,renowned for their cost-effectiveness and non-flammability,have attracted considerable attention in the realm of batteries featuring Zn-based and Sn-based configurations.These configurations employ Z...Aqueous batteries,renowned for their cost-effectiveness and non-flammability,have attracted considerable attention in the realm of batteries featuring Zn-based and Sn-based configurations.These configurations employ Zn and Sn metal anodes,respectively.While the growth patterns of Zn under various current densities have been extensively studied,there has been a scarcity of research on Sn dendrite growth.Our operando imaging analysis reveals that,unlike Zn,Sn forms sharp dendrites at high current density emphasizing the crucial necessity for implementing strategies to suppress the dendrites formation.To address this issue,we introduced a carbon nanotube(CNT)layer on copper foil,effectively preventing the formation of Sn dendrites under high current density,thus enabling the high-current operation of Sn metal batteries.We believe that our work highlights the importance of suppressing dendrite formation in aqueous Sn metal batteries operating at high current density and introduces a fresh perspective on mitigating Sn dendrite formation.展开更多
Aqueous zinc(Zn)-ion batteries(ZIBs)have garnered significant attention as promising energy storage devices,primarily due to their low cost,high power density,and excellent safety profile.However,the commercial viabil...Aqueous zinc(Zn)-ion batteries(ZIBs)have garnered significant attention as promising energy storage devices,primarily due to their low cost,high power density,and excellent safety profile.However,the commercial viability of these batteries is hindered by several issues related to the Zn metal anode,including dendritic growth,hydrogen evolution reaction(HER),surface corrosion,and passivation.This review delves into the root causes and key factors influencing these challenges from both electrochemical thermodynamics and kinetics perspectives.Subsequently,viable strategies to mitigate these issues are systematically summarized,including Zn anode reconstruction,artificial solid-electrolyte interphase(SEI)protection,electrolyte formulation optimization,and separator functionalization.Recent research advancements are examined thoroughly,with a focus on the mechanisms behind these approaches and the resulting battery performance.The review also critically assesses the strengths and limitations of these solutions.Finally,we highlight crucial research directions aimed at advancing the practical application of Zn metal anodes in future aqueous ZIBs.展开更多
The disorganized lithium dendrites and unstable solid electrolyte interphase(SEI)severely impede the practical application of lithium metal batteries(LMBs).Herein,the N-Zn-F coordinated triazine-based covalent organic...The disorganized lithium dendrites and unstable solid electrolyte interphase(SEI)severely impede the practical application of lithium metal batteries(LMBs).Herein,the N-Zn-F coordinated triazine-based covalent organic framework(TTA-COF-ZnF_(2))is fabricated for the first time as an artificial SEI layer on the surface of lithium metal anodes(LMAs)to handle these issues.Zn-N coordination in onedimensional(1D)ordered COF can increase lithiophilic sites,reduce the Li-nucleation barrier,and regulate the Li+local coordination environment by optimizing surface charge density around the Zn metal.The electron-rich state induced by strong electron-withdrawing F-groups constructs electronegative nanochannels,which trigger efficient Li+desolvation.These beneficial attributes boost Li^(+)transfer,and homogenize Li^(+)flux,leading to uniform Li deposition.Besides,the lithiophilic triazine ring polar groups in TTA-COF-ZnF_(2)further facilitate the Li^(+)migration.The latent working mechanism of adjusting Li deposition behaviors and stabilizing LMAs for TTA-COF-ZnF_(2)is illustrated by detailed in-situ/ex-situ characterizations and density functional theory(DFT)calculations.As expected,TTA-COF-ZnF_(2)-modified Li|Cu half cells deliver a higher Coulombic efficiency(CE)of 98.4% over 250 cycles and lower nucleation overpotential(11 mV)at 1 mA cm^(-2),while TTA-COF-ZnF_(2)@Li symmetric cells display a long lifespan over3785 h at 2 mA cm^(-2).The TTA-COF-ZnF_(2)@Li|S full cells exert ultra high capacity retention of 81%(837 mA h g^(-1))after 600 cycles at 1C.Besides,the TTA-COF-ZnF_(2)@Li|LFP full cells with a high loading of 7.1 mg cm^(-2)exert ultrahigh capacity retention of 89%(108 mAh g^(-1))after 700 cycles at 5C.This synergistic strategy in N-Zn-F coordinated triazine-based COF provides a new insight to regulate the uniform platins/stripping behaviors for developing ultra-stable and dendrite-free LMBs.展开更多
The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated...The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.展开更多
Lithium metal is one of the most promising anodes for lithium batteries because of their high theoretical specific capacity and the low electrochemical potential.However,the commercialization of lithium metal anodes(L...Lithium metal is one of the most promising anodes for lithium batteries because of their high theoretical specific capacity and the low electrochemical potential.However,the commercialization of lithium metal anodes(LMAs)is facing significant obstacles,such as uncontrolled lithium dendrite growth and unstable solid electrolyte interface,leading to inferior Coulombic efficiency,unsatisfactory cycling stability and even serious safety issues.Introducing low-cost natural clay-based materials(NCBMs)in LMAs is deemed as one of the most effective methods to solve aforementioned issues.These NCBMs have received considerable attention for stabilizing LMAs due to their unique structure,large specific surface areas,abundant surface groups,high mechanical strength,excellent thermal stability,and environmental friendliness.Considering the rapidly growing research enthusiasm for this topic in the last several years,here,we review the recent progress on the application of NCBMs in stable and dendrite-free LMAs.The different structures and modification methods of natural clays are first summarized.In addition,the relationship between their modification methods and nano/microstructures,as well as their impact on the electrochemical properties of LMAs are systematically discussed.Finally,the current challenges and opportunities for application of NCBMs in stable LMAs are also proposed to facilitate their further development.展开更多
This study presents a novel Li metal host material with a unique hollow nano-spherical structure that incorporates Ag nano-seeds into a graphitic carbon nitride(g-C_(3)N_(4))shell layer,referred to as g-C_(3)N_(4)@Ag ...This study presents a novel Li metal host material with a unique hollow nano-spherical structure that incorporates Ag nano-seeds into a graphitic carbon nitride(g-C_(3)N_(4))shell layer,referred to as g-C_(3)N_(4)@Ag hollow spheres.The g-C_(3)N_(4)@Ag spheres provide a managed internal site for Li metal encapsulation and promote stable Li plating.The g-C_(3)N_(4) spheres are uniformly coated using polydopamine,which has an adhesive nature,to enhance lithium plating/stripping stability.The strategic presence of Ag nano-seeds eliminates the nucleation barrier,properly directing Li growth within the hollow spheres.This design facilitates highly reversible and consistent lithium deposition,offering a promising direction for the production of high-performance lithium metal anodes.These well-designed g-C_(3)N_(4)@Ag hollow spheres ensure stable Li plating/stripping kinetics over more than 500 cycles with a high coulombic efficiency of over 97%.Furthermore,a full cell made using LiNi_(0.90)Co_(0.07)Mn_(0.03)O_(2) and Li-g-C_(3)N_(4)@Ag host electrodes demonstrated highly competitive performance over 200 cycles,providing a guide for the implementation of this technology in advanced lithium metal batteries.展开更多
Sodium metal has been widely studied in the field of batteries due to its high theoretical specific capacity(~1,166 m Ah/g),low redox potential(-2.71 V compared to standard hydrogen electrode),and lowcost advantages.H...Sodium metal has been widely studied in the field of batteries due to its high theoretical specific capacity(~1,166 m Ah/g),low redox potential(-2.71 V compared to standard hydrogen electrode),and lowcost advantages.However,problems such as unstable solid electrolyte interface(SEI),uncontrolled dendrite growth,and side reactions between solid-liquid interfaces have hindered the practical application of sodium metal anodes(SMAs).Currently,lots of strategies have been developed to achieve stabilized sodium metal anodes.Among these strategies,modified metal current collectors(MCCs)stand out due to their unique role in accommodating volumetric fluctuations with superior structure,lowering the energy barrier for sodium nucleation,and providing guided uniform sodium deposition.In this review,we first introduced three common metal-based current collectors applied to SMAs.Then,we summarized strategies to improve sodium deposition behavior by optimally engineering the surface of MCCs,including surface loading,surface structural design,and surface engineering for functional modification.We have followed the latest research progress and summarized surface optimization cases on different MCCs and their applications in battery systems.展开更多
Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,saf...Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries.Current research efforts primarily focus on altering the solvated structure of Li+by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier,expedite the desolvation process,and suppress the growth of lithium dendrites.Nevertheless,an integrated approach that combines the advantages of these two strategies remains elusive.In this study,we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process,reduce the nucleation barrier of Li+,and modulate its solvated structure.This approach enhanced the inorganic compound content in the solid electrolyte interphase(SEI)on lithium foil surfaces,leading to stable Li+deposition and stripping.Specifically,Li||Cu cells demonstrated excellent cycle life and Coulombic efficiency(97.28%and 98.59%,respectively)at 0.5 m A/cm^(2)@0.5 m Ah/cm^(2)and 1 m A/cm^(2)@1 m Ah/cm^(2)for 410 and 240 cycles,respectively.Li||Li symmetrical cells showed no short circuit at 1 m A/cm^(2)@1 m Ah/cm^(2)for 1150 h,and Li||LFP full cells retained 68.9%of their capacity(104.6 m Ah/g)after 250 cycles at N/P(1.1:1.0)with a current density of 1C.展开更多
Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dua...Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dual continuous rapid transport of interfacial electron/ion is required for homogeneous Li deposition.Herein,we propose a strategy to improve the Li metal anode performance by rationally regulating the interfacial electron density and Li ion transport through the SEI film.This key technique involves decreasing the interfacial oxygen density of biomass-derived carbon host by regulating the arrangement of the celluloses precursor fibrils.The higher specific surface area and lower interfacial oxygen density decrease the local current density and ensure the formation of thin and even SEI film,which stabilized Li^(+)transfer through the Li/electrolyte interface.Moreover,the improved graphitization and the interconnected conducting network enhance the surface electronegativity of carbon and enable uninterruptible electron conduction.The result is continuous and rapid coupled interfacial electron/ion transport at the anode/electrolyte reaction interface,which facilitates uniform Li deposition and improves Li anode performance.The Li/C anode shows a high initial Coulombic efficiency of 98%and a long-term lifespan of over 150cycles at a practical low N/P(negative-to-positive)ratio of 1.44 in full cells.展开更多
Aqueous zinc-ion batteries have emerged as promising candidates in next-generation energy storage sys-tems.However,their practical implementation is significantly hindered by interfacial side reactions,par-ticularly t...Aqueous zinc-ion batteries have emerged as promising candidates in next-generation energy storage sys-tems.However,their practical implementation is significantly hindered by interfacial side reactions,par-ticularly the hydrogen evolution reaction(HER)at the Zn metal anode interface.Herein,this study presents an innovative approach to address this challenge through the construction of an interfacial pref-erential coordination layer on the Zn anode surface.The proposed layer effectively terminates the conti-nuity of interfacial hydrogen-bond networks and blocks proton transport,thereby mitigating the HER.Specifically,2-phenylbenzimidazole-5-sulfonic acid(PBSA)with zincophilic groups was introduced as an electrolyte additive,which would be preferentially and selectively anchored on the Zn surface through its zincophilic nitrogen and sulfonic acid,forming the interfacial coordination layer.This coordination layer serves as a protective barrier,repelling water molecules from the Zn electrode surface and alleviat-ing water decomposition.Crucially,the interfacial coordination layer features stronger hydrogen-bonding interactions with interfacial water molecules,terminates the hydrogen-bonding network between water molecules,hinders the transportation and electro-reduction of proton,and ultimately inhibits HER at the interface.As a result,the Zn symmetric cell with PBSA/ZnSO_(4)delivered higher cycling stability of 2500 h at 1 mA cm^(-2)and Zn/NH_(4)V_(4)O_(10)full cells with PBSA/ZnSO_(4)possessed enhanced capac-ity retention.This interfacial hydrogen-bond regulation strategy provided valuable insight for designing HER-free interfacial protective layer in high-performance aqueous batteries.展开更多
The replacement of non-aqueous organic electrolytes with solid-state electrolytes(SSEs)in solid-state lithium metal batteries(SLMBs)is considered a promising strategy to address the constraints of lithium-ion batterie...The replacement of non-aqueous organic electrolytes with solid-state electrolytes(SSEs)in solid-state lithium metal batteries(SLMBs)is considered a promising strategy to address the constraints of lithium-ion batteries,especially in terms of energy density and reliability.Nevertheless,few SLMBs can deliver the required cycling performance and long-term stability for practical use,primarily due to suboptimal interface properties.Given the diverse solidification pathways leading to different interface characteristics,it is crucial to pinpoint the source of interface deterioration and develop appropriate remedies.This review focuses on Li|SSE interface issues between lithium metal anode and SSE,discussing recent advancements in the understanding of(electro)chemistry,the impact of defects,and interface evolutions that vary among different SSE species.The state-ofthe-art strategies concerning modified SEI,artificial interlayer,surface architecture,and composite structure are summarized and delved into the internal relationships between interface characteristics and performance enhancements.The current challenges and opportunities in characterizing and modifying the Li|SSE interface are suggested as potential directions for achieving practical SLMBs.展开更多
Lithium(Li) metal anodes(LMAs) that employ three-dimensional lithiophilic frameworks are among the most promising options for constructing high-energy-density rechargeable batteries.Herein,hollow ZnS nanosheets with t...Lithium(Li) metal anodes(LMAs) that employ three-dimensional lithiophilic frameworks are among the most promising options for constructing high-energy-density rechargeable batteries.Herein,hollow ZnS nanosheets with the coating of N-doped carbon are modified on the surface of carbon cloth(NCHZS@CC) to serve as the host material for Li metal.It is revealed that the high surface area of NCHZS@CC can significantly reduce local current density and mitigate volume change during cycling.More importantly,the lithiated product of ZnS,confined within the carbon cage,facilitates the uniform deposition of Li metal on carbon fibers and promotes the formation of a stable solid electrolyte interphase enriched with Li_(2)S,thereby improving long-term performance as the cycling progresses.Consequently,the LMAs based on NCHZS@CC demonstrate an impressive cycle life beyond560 h with an ultralow overpotential of 38 mV at a current density of 5 mA cm^(-2)with a capacity of 1 mAh cm^(-2)in the symmetric cell.In addition,when matched with a high mass loading cathode of LiFePO_(4)(11.5 mg cm^(-2)),the assembled full cell displays outstanding performance,achieving 900 cycles at a rate of 2C.展开更多
Aqueous zinc-ion batteries(AZIBs)present a promising option for next-generation batteries given their high safety,eco-friendliness,and resource sustainability.Nonetheless,the practical application of zinc anodes is hi...Aqueous zinc-ion batteries(AZIBs)present a promising option for next-generation batteries given their high safety,eco-friendliness,and resource sustainability.Nonetheless,the practical application of zinc anodes is hindered by inevitable parasitic reactions and dendrite growth.Here,zinc alloy layers(i.e.,ZnCo and ZnFe alloys)were rationally constructed on the zinc surface by chemical displacement reactions.The alloying process exposes more(002)planes of the ZnCo anode to guide the preferential and dendrite-free zinc deposition.Furthermore,the ZnCo alloy layer not only effectively inhibits water-induced side reactions but also accelerates electrode kinetics,enabling highly reversible zinc plating/stripping.As a result,the ZnCo anode achieves a Coulombic efficiency of 99.2%over 1300 cycles,and the ZnCo symmetric cell exhibits a long cycle life of over 2000 h at 4.4 mA cm^(-2).Importantly,the ZnCo//NH_(4)V_(4)O_(10)full cell retains a high discharge capacity of 218.4 mAh g^(-1)after 800 cycles.Meanwhile,the ZnFe-based symmetric cell also displays excellent cycling stability over 2500 h at 1.77 mA cm^(-2).This strategy provides a facile anode modification approach toward high-performance AZIBs.展开更多
Lithium metal is a compelling choice as an anode material for high-energy-density batteries,attributed to its elevated theoretical specific energy and low redox potential.Nevertheless,challenges arise due to its susce...Lithium metal is a compelling choice as an anode material for high-energy-density batteries,attributed to its elevated theoretical specific energy and low redox potential.Nevertheless,challenges arise due to its susceptibility to high-volume changes and the tendency for dendritic development during cycling,leading to restricted cycle life and diminished Coulombic efficiency(CE).Here,we innovatively engineered a kind of porous biocarbon to serve as the framework for a lithium metal anode,which boasts a heightened specific surface area and uniformly dispersed ZnO active sites,directly derived from metasequoia cambium.The porous structure efficiently mitigates local current density and alleviates the volume expansion of lithium.Also,incorporating the ZnO lithiophilic site notably reduces the nucleation overpotential to a mere 16 mV,facilitating the deposition of lithium in a compact form.As a result,this innovative material ensures an impressive CE of 98.5%for lithium plating/stripping over 500 cycles,a remarkable cycle life exceeding 1200 h in a Li symmetrical cell,and more than 82%capacity retention ratio after an astonishing 690 cycles in full cells.In all,such a rationally designed Li composite anode effectively mitigates volume change,enhances lithophilicity,and reduces local current density,thereby inhibiting dendrite formation.The preparation of a highperformance lithium anode frame proves the feasibility of using biocarbon in a lithium anode frame.展开更多
Aqueous zinc-ion batteries(AZIBs)are regarded as promising energy storage devices due to their low cost,high capacity,and ecological safety.Nevertheless,the severe dendritic growth and side reactions hinder their prac...Aqueous zinc-ion batteries(AZIBs)are regarded as promising energy storage devices due to their low cost,high capacity,and ecological safety.Nevertheless,the severe dendritic growth and side reactions hinder their practical applicability significantly.Herein,an ultrathin Cu coating layer(~200 nm)is decorated on zinc foils via filtered cathodic vacuum arc deposition technology,aiming to achieve high-performance AZIBs.The Cu layer effectively suppresses chemical corrosion and hydrogen evolution reactions and enables preferential(002)Zn deposition during the stripping/plating cycles.Consequently,the Cu@Zn anode represents an elongated cycle life over 4,000 h at 2 mA·cm^(-2)/2 mAh·cm^(-2).Even in conditions of high current density of 5 and 10 mA·cm^(-2),the Cu@Zn anode shows prolonged cycling stability exceeding 4000 and 2000 h,respectively.Such advantages also bring high Coulombic efficiency of 99.87%under 5 mAh·cm^(-2)in Cu@Ti||Zn half-cell over 1500 cycles.Moreover,the Cu@Zn||MnO_(2)full cell demonstrates a superior cyclability with a specific capacity of 203 mAh·g^(-1)after 500 cycles a1 A·g^(-1).展开更多
The undesirable dendrite growth induced by non-planar zinc(Zn)deposition and low Coulombic efficiency resulting from severe side reactions have been long-standing challenges for metallic Zn anodes and substantially im...The undesirable dendrite growth induced by non-planar zinc(Zn)deposition and low Coulombic efficiency resulting from severe side reactions have been long-standing challenges for metallic Zn anodes and substantially impede the practical application of rechargeable aqueous Zn metal batteries(ZMBs).Herein,we present a strategy for achieving a high-rate and long-cycle-life Zn metal anode by patterning Zn foil surfaces and endowing a Zn-Indium(Zn-In)interface in the microchannels.The accumulation of electrons in the microchannel and the zincophilicity of the Zn-In interface promote preferential heteroepitaxial Zn deposition in the microchannel region and enhance the tolerance of the electrode at high current densities.Meanwhile,electron aggregation accelerates the dissolution of non-(002)plane Zn atoms on the array surface,thereby directing the subsequent homoepitaxial Zn deposition on the array surface.Consequently,the planar dendrite-free Zn deposition and long-term cycling stability are achieved(5,050 h at 10.0 mA cm^(−2) and 27,000 cycles at 20.0 mA cm^(−2)).Furthermore,a Zn/I_(2) full cell assembled by pairing with such an anode can maintain good stability for 3,500 cycles at 5.0 C,demonstrating the application potential of the as-prepared ZnIn anode for high-performance aqueous ZMBs.展开更多
Metallic lithium(Li)is considered the“Holy Grail”anode material for the nextgeneration of Li batteries with high energy density owing to the extraordinary theoretical specific capacity and the lowest negative electr...Metallic lithium(Li)is considered the“Holy Grail”anode material for the nextgeneration of Li batteries with high energy density owing to the extraordinary theoretical specific capacity and the lowest negative electrochemical potential.However,owing to inhomogeneous Li-ion flux,Li anodes undergo uncontrollable Li deposition,leading to limited power output and practical applications.Carbon materials and their composites with controllable structures and properties have received extensive attention to guide the homogeneous growth of Li to achieve high-performance Li anodes.In this review,the correlation between the behavior of Li anode and the properties of carbon materials is proposed.Subsequently,we review emerging strategies for rationally designing high-performance Li anodes with carbon materials,including interface engineering(stabilizing solid electrolyte interphase layer and other functionalized interfacial layer)and architecture design of host carbon(constructing three-dimension structure,preparing hollow structure,introducing lithiophilic sites,optimizing geometric effects,and compositing with Li).Based on the insights,some prospects on critical challenges and possible future research directions in this field are concluded.It is anticipated that further innovative works on the fundamental chemistry and theoretical research of Li anodes are needed.展开更多
Lithium metal batteries with inorganic solid-state electrolytes have emerged as strong and attractive candidates for electrochemical energy storage devices because of their high-energy content and safety.Nonetheless,i...Lithium metal batteries with inorganic solid-state electrolytes have emerged as strong and attractive candidates for electrochemical energy storage devices because of their high-energy content and safety.Nonetheless,inherent challenges of deleterious lithium dendrite growth and poor interfacial stability hinder their commercial application.Herein,we report a liquid metal-coated lithium metal(LM@Li)anode strategy to improve the contact between lithium metal and a Li6PS5Cl inorganic electrolyte.The LM@Li symmetric cell shows over 1000 h of stable lithium plating/stripping cycles at 2mA cm^(-2) and a significantly higher critical current density of 9.8 mAcm^(-2) at 25°C.In addition,a full battery assembled with a high-capacity composite LiNbO3@-LiNi_(0.7)Co_(0.2)Mn_(0.1)O_(2)(LNO@NCM721)cathode shows stable cycling performance.Experimental and computational results have demonstrated that dendrite growth tolerance and physical contact in solid-state batteries can be reinforced by using LM interlayers for interfacial modification.展开更多
基金financially supported by the Science and Technology Development Project of Henan Province,China(No.242102241042)the Joint Fund of Henan Province Science and Technology R&D Program(No.225200810093)+1 种基金the Startup Research of Henan Academy of Sciences(No.231817001)the Key Innovation Projects for Postgraduates of Henan Academy of Sciences(No.24331712)。
文摘Aqueous zinc-ion batteries are regarded as promising electrochemical energy-storage systems for various applications because of their high safety,low costs,and high capacities.However,dendrite formation and side reactions during zinc plating or stripping greatly reduce the capacity and cycle life of a battery and subsequently limit its practical application.To address these issues,we modified the surface of a zinc anode with a functional bilayer composed of zincophilic Cu and flexible polymer layers.The zincophilic Cu interfacial layer was prepared through CuSO_(4)solution pretreatment to serve as a nucleation site to facilitate uniform Zn deposition.Meanwhile,the polymer layer was coated onto the Cu interface layer to serve as a protective layer that would prevent side reactions between zinc and electrolytes.Benefiting from the synergistic effect of the zincophilic Cu and protective polymer layers,the symmetric battery exhibits an impressive cycle life,lasting over 2900 h at a current density of 1 m A·cm^(-2)with a capacity of 1 m A·h·cm^(-2).Moreover,a full battery paired with a vanadium oxide cathode achieves a remarkable capacity retention of 72%even after 500 cycles.
基金support from the National Natural Science Foundation of China(No.U2333210)the Sichuan Science and Technology Program,China(No.21SYSX0011)。
文摘Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the solid-electrolyte interphase(SEI)during extended cycling use may result in dendrite growth,which can penetrate the separator and pose significant short-circuit risks.Forming a stable SEI is essential for the long-term operation of the batteries.Fluorine-rich SEI has garnered significant attention for its ability to effectively passivate electrodes,regulate lithium deposition,and inhibit electrolyte corrosion.Understanding the structural components and preparation methods of existing fluorinated SEI is crucial for optimizing lithium metal anode performance.This paper reviews the research on optimizing LiF passivation interfaces to protect lithium metal anodes.It focuses on four types of compositions in fluorinated SEI that work synergistically to enhance SEI performance.For instance,combining compounds with LiF can further enhance the mechanical strength and ionic conductivity of the SEI.Integrating metals with LiF significantly improves electrochemical performance at the SEI/anode interface,with a necessary focus on reducing electron tunneling risks.Additionally,incorporating polymers with LiF offers balanced improvements in interfacial toughness and ionic conductivity,though maintaining structural stability over long cycles remains a critical area for future research.Although alloys combined with LiF increase surface energy and lithium affinity,challenges such as dendrite growth and volume expansion persist.In summary,this paper emphasizes the crucial role of interfacial structures in LMBs and offers comprehensive guidance for future design and development efforts in battery technology.
基金supported by the Institute for Basic Science,south korea(IBS-R006-A2)supproted by the Basic Science Research Program through the National Research Foundation of Korea(NRF),south korea funded by the Ministry of Education(2018R1D1A3B05042787)+1 种基金supported by the National Research Foundation of Korea(NRF),south korea grant funded by the Korea Government(MSIT)(RS-2025-00518953)the National Research Foundation of Korea(NRF),south korea grant funded by the Korea Government(MSIT)(RS-202400422387)。
文摘Aqueous batteries,renowned for their cost-effectiveness and non-flammability,have attracted considerable attention in the realm of batteries featuring Zn-based and Sn-based configurations.These configurations employ Zn and Sn metal anodes,respectively.While the growth patterns of Zn under various current densities have been extensively studied,there has been a scarcity of research on Sn dendrite growth.Our operando imaging analysis reveals that,unlike Zn,Sn forms sharp dendrites at high current density emphasizing the crucial necessity for implementing strategies to suppress the dendrites formation.To address this issue,we introduced a carbon nanotube(CNT)layer on copper foil,effectively preventing the formation of Sn dendrites under high current density,thus enabling the high-current operation of Sn metal batteries.We believe that our work highlights the importance of suppressing dendrite formation in aqueous Sn metal batteries operating at high current density and introduces a fresh perspective on mitigating Sn dendrite formation.
基金financial support by the open foundation of State Key Laboratory of Chemical Engineering(SKL-Ch E-24B03)the Natural Science Foundation of Shandong Province,China(ZR2021QE098)financial support from the Start-Up Research Fund from the University of Macao(SRG2024-00034-IAPME).
文摘Aqueous zinc(Zn)-ion batteries(ZIBs)have garnered significant attention as promising energy storage devices,primarily due to their low cost,high power density,and excellent safety profile.However,the commercial viability of these batteries is hindered by several issues related to the Zn metal anode,including dendritic growth,hydrogen evolution reaction(HER),surface corrosion,and passivation.This review delves into the root causes and key factors influencing these challenges from both electrochemical thermodynamics and kinetics perspectives.Subsequently,viable strategies to mitigate these issues are systematically summarized,including Zn anode reconstruction,artificial solid-electrolyte interphase(SEI)protection,electrolyte formulation optimization,and separator functionalization.Recent research advancements are examined thoroughly,with a focus on the mechanisms behind these approaches and the resulting battery performance.The review also critically assesses the strengths and limitations of these solutions.Finally,we highlight crucial research directions aimed at advancing the practical application of Zn metal anodes in future aqueous ZIBs.
基金financially supported by the National Natural Science Foundation of China(52472093,52176185)the Department of Science and Technology of Hubei Province of China(2022CFA069,2022BAA086)。
文摘The disorganized lithium dendrites and unstable solid electrolyte interphase(SEI)severely impede the practical application of lithium metal batteries(LMBs).Herein,the N-Zn-F coordinated triazine-based covalent organic framework(TTA-COF-ZnF_(2))is fabricated for the first time as an artificial SEI layer on the surface of lithium metal anodes(LMAs)to handle these issues.Zn-N coordination in onedimensional(1D)ordered COF can increase lithiophilic sites,reduce the Li-nucleation barrier,and regulate the Li+local coordination environment by optimizing surface charge density around the Zn metal.The electron-rich state induced by strong electron-withdrawing F-groups constructs electronegative nanochannels,which trigger efficient Li+desolvation.These beneficial attributes boost Li^(+)transfer,and homogenize Li^(+)flux,leading to uniform Li deposition.Besides,the lithiophilic triazine ring polar groups in TTA-COF-ZnF_(2)further facilitate the Li^(+)migration.The latent working mechanism of adjusting Li deposition behaviors and stabilizing LMAs for TTA-COF-ZnF_(2)is illustrated by detailed in-situ/ex-situ characterizations and density functional theory(DFT)calculations.As expected,TTA-COF-ZnF_(2)-modified Li|Cu half cells deliver a higher Coulombic efficiency(CE)of 98.4% over 250 cycles and lower nucleation overpotential(11 mV)at 1 mA cm^(-2),while TTA-COF-ZnF_(2)@Li symmetric cells display a long lifespan over3785 h at 2 mA cm^(-2).The TTA-COF-ZnF_(2)@Li|S full cells exert ultra high capacity retention of 81%(837 mA h g^(-1))after 600 cycles at 1C.Besides,the TTA-COF-ZnF_(2)@Li|LFP full cells with a high loading of 7.1 mg cm^(-2)exert ultrahigh capacity retention of 89%(108 mAh g^(-1))after 700 cycles at 5C.This synergistic strategy in N-Zn-F coordinated triazine-based COF provides a new insight to regulate the uniform platins/stripping behaviors for developing ultra-stable and dendrite-free LMBs.
基金financially supported by Jilin Province Science and Technology Department Program(Nos.YDZJ202201ZYTS304,20220201130GX and 20240101004JJ)the National Natural Science Foundation of China(Nos.52171210 and 52471229)the Science and Technology Project of Jilin Provincial Education Department(No.JJKH20220428KJ)
文摘The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.
基金supported by the Henan Province Science and Technology Research Project(No.232102241006)the National Key Research and Development Program of China(No.2020YFB1713500)+2 种基金Opening Project of National Joint Engineering Research Center for Abrasion Control and Molding of Metal Materials&Henan Key Laboratory of High-temperature Structural and Functional Materials,Henan University of Science and Technology(No.HKDNM2019013)the Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210)the Major Science and Technology Projects of Henan Province(No.221100230200)。
文摘Lithium metal is one of the most promising anodes for lithium batteries because of their high theoretical specific capacity and the low electrochemical potential.However,the commercialization of lithium metal anodes(LMAs)is facing significant obstacles,such as uncontrolled lithium dendrite growth and unstable solid electrolyte interface,leading to inferior Coulombic efficiency,unsatisfactory cycling stability and even serious safety issues.Introducing low-cost natural clay-based materials(NCBMs)in LMAs is deemed as one of the most effective methods to solve aforementioned issues.These NCBMs have received considerable attention for stabilizing LMAs due to their unique structure,large specific surface areas,abundant surface groups,high mechanical strength,excellent thermal stability,and environmental friendliness.Considering the rapidly growing research enthusiasm for this topic in the last several years,here,we review the recent progress on the application of NCBMs in stable and dendrite-free LMAs.The different structures and modification methods of natural clays are first summarized.In addition,the relationship between their modification methods and nano/microstructures,as well as their impact on the electrochemical properties of LMAs are systematically discussed.Finally,the current challenges and opportunities for application of NCBMs in stable LMAs are also proposed to facilitate their further development.
基金supported by the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(No.GTL24011-000)supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2023-00272863)supported by Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea Government(MOTIE)(P0012748,HRD Program for Industrial Innovation)。
文摘This study presents a novel Li metal host material with a unique hollow nano-spherical structure that incorporates Ag nano-seeds into a graphitic carbon nitride(g-C_(3)N_(4))shell layer,referred to as g-C_(3)N_(4)@Ag hollow spheres.The g-C_(3)N_(4)@Ag spheres provide a managed internal site for Li metal encapsulation and promote stable Li plating.The g-C_(3)N_(4) spheres are uniformly coated using polydopamine,which has an adhesive nature,to enhance lithium plating/stripping stability.The strategic presence of Ag nano-seeds eliminates the nucleation barrier,properly directing Li growth within the hollow spheres.This design facilitates highly reversible and consistent lithium deposition,offering a promising direction for the production of high-performance lithium metal anodes.These well-designed g-C_(3)N_(4)@Ag hollow spheres ensure stable Li plating/stripping kinetics over more than 500 cycles with a high coulombic efficiency of over 97%.Furthermore,a full cell made using LiNi_(0.90)Co_(0.07)Mn_(0.03)O_(2) and Li-g-C_(3)N_(4)@Ag host electrodes demonstrated highly competitive performance over 200 cycles,providing a guide for the implementation of this technology in advanced lithium metal batteries.
基金supported by the National Natural Science Foundation of China(Nos.52102291,52271011,and 51701142)supported by a grant from the Cangzhou Institute of Tiangong University(No.TGCYY-F-0201)。
文摘Sodium metal has been widely studied in the field of batteries due to its high theoretical specific capacity(~1,166 m Ah/g),low redox potential(-2.71 V compared to standard hydrogen electrode),and lowcost advantages.However,problems such as unstable solid electrolyte interface(SEI),uncontrolled dendrite growth,and side reactions between solid-liquid interfaces have hindered the practical application of sodium metal anodes(SMAs).Currently,lots of strategies have been developed to achieve stabilized sodium metal anodes.Among these strategies,modified metal current collectors(MCCs)stand out due to their unique role in accommodating volumetric fluctuations with superior structure,lowering the energy barrier for sodium nucleation,and providing guided uniform sodium deposition.In this review,we first introduced three common metal-based current collectors applied to SMAs.Then,we summarized strategies to improve sodium deposition behavior by optimally engineering the surface of MCCs,including surface loading,surface structural design,and surface engineering for functional modification.We have followed the latest research progress and summarized surface optimization cases on different MCCs and their applications in battery systems.
基金supported by Yunnan Natural Science Foundation Project(No.202202AG050003)Yunnan Fundamental Research Projects(Nos.202101BE070001-018 and 202201AT070070)+1 种基金the National Youth Talent Support Program of Yunnan Province China(No.YNQR-QNRC-2020-011)Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects(No.2023-XMDJ-00617107)。
文摘Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries.Current research efforts primarily focus on altering the solvated structure of Li+by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier,expedite the desolvation process,and suppress the growth of lithium dendrites.Nevertheless,an integrated approach that combines the advantages of these two strategies remains elusive.In this study,we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process,reduce the nucleation barrier of Li+,and modulate its solvated structure.This approach enhanced the inorganic compound content in the solid electrolyte interphase(SEI)on lithium foil surfaces,leading to stable Li+deposition and stripping.Specifically,Li||Cu cells demonstrated excellent cycle life and Coulombic efficiency(97.28%and 98.59%,respectively)at 0.5 m A/cm^(2)@0.5 m Ah/cm^(2)and 1 m A/cm^(2)@1 m Ah/cm^(2)for 410 and 240 cycles,respectively.Li||Li symmetrical cells showed no short circuit at 1 m A/cm^(2)@1 m Ah/cm^(2)for 1150 h,and Li||LFP full cells retained 68.9%of their capacity(104.6 m Ah/g)after 250 cycles at N/P(1.1:1.0)with a current density of 1C.
基金supported by the National Natural Science Foundation of China(21975091,22122902,and 52272208)the Fundamental Research Fund for the Central Universities of China(2662023LXPY001 and 2662021JC004).
文摘Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dual continuous rapid transport of interfacial electron/ion is required for homogeneous Li deposition.Herein,we propose a strategy to improve the Li metal anode performance by rationally regulating the interfacial electron density and Li ion transport through the SEI film.This key technique involves decreasing the interfacial oxygen density of biomass-derived carbon host by regulating the arrangement of the celluloses precursor fibrils.The higher specific surface area and lower interfacial oxygen density decrease the local current density and ensure the formation of thin and even SEI film,which stabilized Li^(+)transfer through the Li/electrolyte interface.Moreover,the improved graphitization and the interconnected conducting network enhance the surface electronegativity of carbon and enable uninterruptible electron conduction.The result is continuous and rapid coupled interfacial electron/ion transport at the anode/electrolyte reaction interface,which facilitates uniform Li deposition and improves Li anode performance.The Li/C anode shows a high initial Coulombic efficiency of 98%and a long-term lifespan of over 150cycles at a practical low N/P(negative-to-positive)ratio of 1.44 in full cells.
基金supported by financial support from the National Natural Science Foundation of China(Grant No.22225801 and 22461142137).
文摘Aqueous zinc-ion batteries have emerged as promising candidates in next-generation energy storage sys-tems.However,their practical implementation is significantly hindered by interfacial side reactions,par-ticularly the hydrogen evolution reaction(HER)at the Zn metal anode interface.Herein,this study presents an innovative approach to address this challenge through the construction of an interfacial pref-erential coordination layer on the Zn anode surface.The proposed layer effectively terminates the conti-nuity of interfacial hydrogen-bond networks and blocks proton transport,thereby mitigating the HER.Specifically,2-phenylbenzimidazole-5-sulfonic acid(PBSA)with zincophilic groups was introduced as an electrolyte additive,which would be preferentially and selectively anchored on the Zn surface through its zincophilic nitrogen and sulfonic acid,forming the interfacial coordination layer.This coordination layer serves as a protective barrier,repelling water molecules from the Zn electrode surface and alleviat-ing water decomposition.Crucially,the interfacial coordination layer features stronger hydrogen-bonding interactions with interfacial water molecules,terminates the hydrogen-bonding network between water molecules,hinders the transportation and electro-reduction of proton,and ultimately inhibits HER at the interface.As a result,the Zn symmetric cell with PBSA/ZnSO_(4)delivered higher cycling stability of 2500 h at 1 mA cm^(-2)and Zn/NH_(4)V_(4)O_(10)full cells with PBSA/ZnSO_(4)possessed enhanced capac-ity retention.This interfacial hydrogen-bond regulation strategy provided valuable insight for designing HER-free interfacial protective layer in high-performance aqueous batteries.
基金Financial support from National Key R&D Program(2022YFB2404600)Natural Science Foundation of China(Key Project of 52131306)+1 种基金Project on Carbon Emission Peak and Neutrality of Jiangsu Province(BE2022031-4)the Big Data Computing Center of Southeast University are greatly appreciated.
文摘The replacement of non-aqueous organic electrolytes with solid-state electrolytes(SSEs)in solid-state lithium metal batteries(SLMBs)is considered a promising strategy to address the constraints of lithium-ion batteries,especially in terms of energy density and reliability.Nevertheless,few SLMBs can deliver the required cycling performance and long-term stability for practical use,primarily due to suboptimal interface properties.Given the diverse solidification pathways leading to different interface characteristics,it is crucial to pinpoint the source of interface deterioration and develop appropriate remedies.This review focuses on Li|SSE interface issues between lithium metal anode and SSE,discussing recent advancements in the understanding of(electro)chemistry,the impact of defects,and interface evolutions that vary among different SSE species.The state-ofthe-art strategies concerning modified SEI,artificial interlayer,surface architecture,and composite structure are summarized and delved into the internal relationships between interface characteristics and performance enhancements.The current challenges and opportunities in characterizing and modifying the Li|SSE interface are suggested as potential directions for achieving practical SLMBs.
基金financial supports from the National Natural Science Foundation of China(Nos.22279116 and U20A20253)the Natural Science Foundation of Zhejiang Province(Nos.LQ24E020012 and LD22E020006)Jianbing Science and Technology Project of Zhejiang Province(No.2023C01127)
文摘Lithium(Li) metal anodes(LMAs) that employ three-dimensional lithiophilic frameworks are among the most promising options for constructing high-energy-density rechargeable batteries.Herein,hollow ZnS nanosheets with the coating of N-doped carbon are modified on the surface of carbon cloth(NCHZS@CC) to serve as the host material for Li metal.It is revealed that the high surface area of NCHZS@CC can significantly reduce local current density and mitigate volume change during cycling.More importantly,the lithiated product of ZnS,confined within the carbon cage,facilitates the uniform deposition of Li metal on carbon fibers and promotes the formation of a stable solid electrolyte interphase enriched with Li_(2)S,thereby improving long-term performance as the cycling progresses.Consequently,the LMAs based on NCHZS@CC demonstrate an impressive cycle life beyond560 h with an ultralow overpotential of 38 mV at a current density of 5 mA cm^(-2)with a capacity of 1 mAh cm^(-2)in the symmetric cell.In addition,when matched with a high mass loading cathode of LiFePO_(4)(11.5 mg cm^(-2)),the assembled full cell displays outstanding performance,achieving 900 cycles at a rate of 2C.
基金supported by the Prospective Basic Research Projects of CNPC(Grant Nos.2022DJ5406,2022DJ5407,2022DJ5408,2022DJ4507,TGRI-2021-1,2022DQ03-03).
文摘Aqueous zinc-ion batteries(AZIBs)present a promising option for next-generation batteries given their high safety,eco-friendliness,and resource sustainability.Nonetheless,the practical application of zinc anodes is hindered by inevitable parasitic reactions and dendrite growth.Here,zinc alloy layers(i.e.,ZnCo and ZnFe alloys)were rationally constructed on the zinc surface by chemical displacement reactions.The alloying process exposes more(002)planes of the ZnCo anode to guide the preferential and dendrite-free zinc deposition.Furthermore,the ZnCo alloy layer not only effectively inhibits water-induced side reactions but also accelerates electrode kinetics,enabling highly reversible zinc plating/stripping.As a result,the ZnCo anode achieves a Coulombic efficiency of 99.2%over 1300 cycles,and the ZnCo symmetric cell exhibits a long cycle life of over 2000 h at 4.4 mA cm^(-2).Importantly,the ZnCo//NH_(4)V_(4)O_(10)full cell retains a high discharge capacity of 218.4 mAh g^(-1)after 800 cycles.Meanwhile,the ZnFe-based symmetric cell also displays excellent cycling stability over 2500 h at 1.77 mA cm^(-2).This strategy provides a facile anode modification approach toward high-performance AZIBs.
基金supported by the National Natural Science Foundation of China(22179005,92372207)Fundamental Research Funds for the Central Universities(2022CX01017).
文摘Lithium metal is a compelling choice as an anode material for high-energy-density batteries,attributed to its elevated theoretical specific energy and low redox potential.Nevertheless,challenges arise due to its susceptibility to high-volume changes and the tendency for dendritic development during cycling,leading to restricted cycle life and diminished Coulombic efficiency(CE).Here,we innovatively engineered a kind of porous biocarbon to serve as the framework for a lithium metal anode,which boasts a heightened specific surface area and uniformly dispersed ZnO active sites,directly derived from metasequoia cambium.The porous structure efficiently mitigates local current density and alleviates the volume expansion of lithium.Also,incorporating the ZnO lithiophilic site notably reduces the nucleation overpotential to a mere 16 mV,facilitating the deposition of lithium in a compact form.As a result,this innovative material ensures an impressive CE of 98.5%for lithium plating/stripping over 500 cycles,a remarkable cycle life exceeding 1200 h in a Li symmetrical cell,and more than 82%capacity retention ratio after an astonishing 690 cycles in full cells.In all,such a rationally designed Li composite anode effectively mitigates volume change,enhances lithophilicity,and reduces local current density,thereby inhibiting dendrite formation.The preparation of a highperformance lithium anode frame proves the feasibility of using biocarbon in a lithium anode frame.
基金supported by the National Natural Science Foundation of China(Nos.52271117 and12027813)Hunan Provincial Natural Science Foundation of China(No.2021JJ30646)the High Technology Research and Development Program of Hunan Province of China(No.2022GK4038).
文摘Aqueous zinc-ion batteries(AZIBs)are regarded as promising energy storage devices due to their low cost,high capacity,and ecological safety.Nevertheless,the severe dendritic growth and side reactions hinder their practical applicability significantly.Herein,an ultrathin Cu coating layer(~200 nm)is decorated on zinc foils via filtered cathodic vacuum arc deposition technology,aiming to achieve high-performance AZIBs.The Cu layer effectively suppresses chemical corrosion and hydrogen evolution reactions and enables preferential(002)Zn deposition during the stripping/plating cycles.Consequently,the Cu@Zn anode represents an elongated cycle life over 4,000 h at 2 mA·cm^(-2)/2 mAh·cm^(-2).Even in conditions of high current density of 5 and 10 mA·cm^(-2),the Cu@Zn anode shows prolonged cycling stability exceeding 4000 and 2000 h,respectively.Such advantages also bring high Coulombic efficiency of 99.87%under 5 mAh·cm^(-2)in Cu@Ti||Zn half-cell over 1500 cycles.Moreover,the Cu@Zn||MnO_(2)full cell demonstrates a superior cyclability with a specific capacity of 203 mAh·g^(-1)after 500 cycles a1 A·g^(-1).
基金supported by the National Research Foundation of Korea Grant funded by the Korean government(MSIP)(No.2018R1A6A1A03025708).
文摘The undesirable dendrite growth induced by non-planar zinc(Zn)deposition and low Coulombic efficiency resulting from severe side reactions have been long-standing challenges for metallic Zn anodes and substantially impede the practical application of rechargeable aqueous Zn metal batteries(ZMBs).Herein,we present a strategy for achieving a high-rate and long-cycle-life Zn metal anode by patterning Zn foil surfaces and endowing a Zn-Indium(Zn-In)interface in the microchannels.The accumulation of electrons in the microchannel and the zincophilicity of the Zn-In interface promote preferential heteroepitaxial Zn deposition in the microchannel region and enhance the tolerance of the electrode at high current densities.Meanwhile,electron aggregation accelerates the dissolution of non-(002)plane Zn atoms on the array surface,thereby directing the subsequent homoepitaxial Zn deposition on the array surface.Consequently,the planar dendrite-free Zn deposition and long-term cycling stability are achieved(5,050 h at 10.0 mA cm^(−2) and 27,000 cycles at 20.0 mA cm^(−2)).Furthermore,a Zn/I_(2) full cell assembled by pairing with such an anode can maintain good stability for 3,500 cycles at 5.0 C,demonstrating the application potential of the as-prepared ZnIn anode for high-performance aqueous ZMBs.
基金supported by the China Petrochemical Corporation(222260).
文摘Metallic lithium(Li)is considered the“Holy Grail”anode material for the nextgeneration of Li batteries with high energy density owing to the extraordinary theoretical specific capacity and the lowest negative electrochemical potential.However,owing to inhomogeneous Li-ion flux,Li anodes undergo uncontrollable Li deposition,leading to limited power output and practical applications.Carbon materials and their composites with controllable structures and properties have received extensive attention to guide the homogeneous growth of Li to achieve high-performance Li anodes.In this review,the correlation between the behavior of Li anode and the properties of carbon materials is proposed.Subsequently,we review emerging strategies for rationally designing high-performance Li anodes with carbon materials,including interface engineering(stabilizing solid electrolyte interphase layer and other functionalized interfacial layer)and architecture design of host carbon(constructing three-dimension structure,preparing hollow structure,introducing lithiophilic sites,optimizing geometric effects,and compositing with Li).Based on the insights,some prospects on critical challenges and possible future research directions in this field are concluded.It is anticipated that further innovative works on the fundamental chemistry and theoretical research of Li anodes are needed.
基金financially supported by the Shenzhen Science and Technology Program (Grant No.KQTD20200820113045083,ZDSYS20190902093220279,and JCYJ20220818102403007)the National Natural Science Foundation of China (52201257)the Shenzhen Research Fund for Returned Scholars (DD11409017).
文摘Lithium metal batteries with inorganic solid-state electrolytes have emerged as strong and attractive candidates for electrochemical energy storage devices because of their high-energy content and safety.Nonetheless,inherent challenges of deleterious lithium dendrite growth and poor interfacial stability hinder their commercial application.Herein,we report a liquid metal-coated lithium metal(LM@Li)anode strategy to improve the contact between lithium metal and a Li6PS5Cl inorganic electrolyte.The LM@Li symmetric cell shows over 1000 h of stable lithium plating/stripping cycles at 2mA cm^(-2) and a significantly higher critical current density of 9.8 mAcm^(-2) at 25°C.In addition,a full battery assembled with a high-capacity composite LiNbO3@-LiNi_(0.7)Co_(0.2)Mn_(0.1)O_(2)(LNO@NCM721)cathode shows stable cycling performance.Experimental and computational results have demonstrated that dendrite growth tolerance and physical contact in solid-state batteries can be reinforced by using LM interlayers for interfacial modification.
