Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmemb...Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmembrane cascade transport mechanism of biological ion pumps,we design a biomimetic dual-cascade separator(BDS)based on gradient pore core–shell Gd_(2)O_(3)@ZIF-7 nanoparticles to stabilize Li metal anodes.The mesoporous Gd_(2)O_(3)core,via Lewis acidic surface,weakens Li^(+) -solvent interactions,thereby reconstructing the solvation structure and achieving pre-desolvation.The microporous ZIF-7 shell then promotes final desolvation through strong confinement effect and N-rich site coordination,while its nanochannels homogenize Li^(+) transport.This synergistic meso/microporous gradient creates a unique dual-cascade effect for ion desolvation and transport.Consequently,BDS achieves a low desolvation energy barrier,a high Li^(+) transference number(0.71),and dendrite-free Li deposition.The average Coulombic efficiency rises from 72.7%to 98.4%,the cycling performance of the Li||Li symmetrical cell improves by 3.2 times,and the capacity retention of LiFePO_4(LFP)||Li full cell increases from 38.3%to73.4%after 500 cycles.This work offers a novel separator design concept,deepens Li deposition understanding,and guides separators from passive protection to active regulation.展开更多
The development of aqueous zinc batteries(AZBs)is severely constrained by uncontrolled dendrite growth and parasitic interfacial reactions.Conventional solvation-dominated additives can mitigate these issues by alteri...The development of aqueous zinc batteries(AZBs)is severely constrained by uncontrolled dendrite growth and parasitic interfacial reactions.Conventional solvation-dominated additives can mitigate these issues by altering the Zn^(2+)solvation structure,but they often compromise ion transport.Here,we introduce a molecular design principle for a non-solvating additive(NSA)based on inductive effects.Ethyl trifluoroacetate(ETFA),obtained by introducing an electron-withdrawing–CF_(3) group adjacent to the–C=O moiety of ethyl acetate(EA),participates minimally in the solvation structure but preferentially undergoes Gibbs adsorption at the Zn-electrolyte interface.This process reduces interfacial tension,reconstructs the electrical double layer,and orients ETFA molecules such that the hydrophilic–C=O groups face the electrolyte,modulating hydrogen-bonding networks,while the hydrophobic–CF_(3) groups anchor onto Zn to regulate deposition.As a result,dendrite formation and side reactions are simultaneously suppressed.With only 1 vol%ETFA,Zn-Cu cells achieve over 4000 stable cycles with 99.89%Coulombic efficiency.Zn-I_(2) full cells employing the modified electrolyte maintain stable operation for more than 500 cycles(6.8 mg cm^(-2),10μm Zn,N/P=2.86),and 0.3 Ah Zn-I_(2) pouch cells(30 mg cm^(-2),100μm Zn)can cycle stably for over 200 cycles.These findings highlight the critical role of Gibbs adsorption in interfacial regulation and provide insights for the molecular design of high-performance additives for stable Zn anodes.展开更多
The practical use of lithium metal anodes(LMAs)is impeded by uncontrolled dendrite growth,primarily caused by uneven Li-ion flux and significant volume changes during cycling.To overcome these challenges,we present bi...The practical use of lithium metal anodes(LMAs)is impeded by uncontrolled dendrite growth,primarily caused by uneven Li-ion flux and significant volume changes during cycling.To overcome these challenges,we present binder-free holey wrinkled-multilayered graphene(HWMG)scaffolds for highperformance LMAs with long cycle life.Holey graphene oxide(HGO)sheets were restacked into particle-like holey wrinkled-multilayered graphene oxide(HWMGO)in a high-concentration GO suspension,in which few-layer HGOs were quickly stabilized and wrinkled during the drying process,and upon reduction,they transformed into HWMG.HWMG exhibited excellent adhesion due to chemical interactions via edge-located functional groups.Its particle-like morphology,with numerous nanopores and high porosity,conferred outstanding mechanical flexibility and low tortuosity,enabling uniform Li-ion flux,buffering volume expansion,and suppressing dendrite growth.As a result,excellent long-term stability over 800 cycles and a voltage hysteresis of ca.7 mV over 6000 h were realized for the HWMG scaffolds,and a high areal capacity of 3.34 mAh cm^(-2) at 0.3 C after 350 cycles was demonstrated in a full-cell configuration.This work promotes the practical application of LMAs by offering a scalable scaffold design that suppresses dendrites and enhances cycle life.展开更多
Aqueous zinc-ion batteries(AZIBs)are considered promising for safe,low-cost,and sustainable energy storage.However,their practical deployment is critically hindered by dendrite formation and parasitic reactions at the...Aqueous zinc-ion batteries(AZIBs)are considered promising for safe,low-cost,and sustainable energy storage.However,their practical deployment is critically hindered by dendrite formation and parasitic reactions at the Zn anode-electrolyte interface.To address this challenge,we present a self-assembly strategy to construct vertically aligned organic-inorganic hybrid nanosheet arrays composed of polyethyleneimine-zinc hydroxide sulfate(PEI-ZHS)via a simple coating-immersion method.The protonation of polyethyleneimine in ZnSO_(4) electrolyte provides localized alkaline conditions for controlled nucleation and growth of ZHS nanosheets at the anode interfa ce.This vertically aligned na noarchitectu re allows for fast Zn^(2+)transport and even nucleation by providing abundant oriented ion-conductive microchannels and accelerating desolvation.Benefiting from these characteristics,the PEI-ZHS layer effectively mitigates side reactions and dendrite growth.As a result,the modified zinc anodes achieve excellent cycling lifespans of 5200 and 1200 h at 1 mA cm^(-2)/1 mAh cm^(-2) and 5 mA cm^(-2)/5 mAh cm^(-2),respectively,in symmetric cells.The Zn‖I_(2) full cell also shows great reversibility,retaining 93.02%of initial capacity after 4000 cycles at 1 A g^(-1).This work introduces a thermodynamically guided and scalable interfacial engineering approach that advances the stability and performance of Zn metal anodes in AZIBs.展开更多
As an earth-abundant and natural biopolymer,cellulose has received significant attention in aqueous zinc-ion batteries(AZIBs)due to its inherent sustainability and non-toxicity,aligning perfectly with the core advanta...As an earth-abundant and natural biopolymer,cellulose has received significant attention in aqueous zinc-ion batteries(AZIBs)due to its inherent sustainability and non-toxicity,aligning perfectly with the core advantages of AZIBs.Nevertheless,the practical implementation of cellulose-based materials is limited by their intrinsically low ionic conductivity.Herein,we introduce a novel zincophilic artificial protective layer by strategically hybridizing hydroxypropyl cellulose(HPC)with zinc trifluoromethanesulfonate on a zinc metal anode(HZ@Zn).Characterization and calculations demonstrate that the multihydroxyl architecture of HPC constructs hydrogen bond networks,whereas the Zn^(2+)-coordinated HPC domains function as preferential nucleation sites for zinc deposition.These interactions collectively enhance ion transport and accelerate desolvation kinetics.Additionally,the hybrid layer's mechanical flexibility and interfacial adhesion ensure the integrity of the artificial protective layer during long cycling.Thanks to this synergistic effect,HZ@Zn shows exceptional electrochemical performance,including a low desolvation activation energy of 14.38 kJ mol^(-1)and ultra-long cycling stability.Symmetric cells demonstrate exceptional longevity,exceeding 9,500 h at 0.5 mA cm^(-2)/0.25 mAh cm^(-2),whereas HZ@Zn‖PANI full cells maintain 89.8%capacity retention after 4000 cycles at 5 A g^(-1).This study establishes biopolymers as versatile platforms for effectively stabilizing the zinc metal anode.展开更多
Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical proper...Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.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 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
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
A fatal issue of Zn-based electrochemical energy storage is uneven Zn^(2+)deposition on the Zn metal anode.Unfortunately,the modulation for the inherent electric field,the origin of driving force for ion diffusion,has...A fatal issue of Zn-based electrochemical energy storage is uneven Zn^(2+)deposition on the Zn metal anode.Unfortunately,the modulation for the inherent electric field,the origin of driving force for ion diffusion,has been given insufficient importance.Herein,the redistribution of the surrounding electric field is demonstrated to depend on the permittivity of the surface medium for the first time,where highpermittivity particles can simultaneously enhance vertical components and reduce horizontal components of the electric field through polarization.Consequently,a bacterial cellulose-based separator is proposed by incorporating a high-permittivity surface medium.Cellulose serves as a robust substrate with a rather low thickness to enable homogeneous dispersion of high-permittivity particles on the surface,which can regulate the localized electric field to guide even Zn deposition by inhibiting twodimensional(2D)Zn^(2+)diffusion and suppressing side reactions by repulsing anion migration toward the Zn anode.The separator achieves significantly enhanced Zn anode stability of 2880 h at 1 mA cm^(-2)and a cumulative capacity of 3.5 Ah cm^(-2)at 10 mA cm^(-2).It also enables a long-term lifespan of 50,000 cycles in Zn||AC capacitor and 1000 cycles at a limited negative/positive(N/P)ratio of 3:1.This work provides a new view to stabilize Zn anode by electric field modulation.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
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
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
The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research.However,the practical implementation of lithium metal anodes is impeded b...The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research.However,the practical implementation of lithium metal anodes is impeded by challenges such as dendrite formation and the inherent instability of the native oxide layer.This study introduces a novel liquid-source plasma technique to create a high-quality solid electrolyte interphase(SEI)composed of LiBr and LiBO_(2).According to first-principal calculation,LiBO_(2)optimizes the electrochemical dynamics and LiBr improves Li diffusion at the interfaces,thus protecting the Li metal from severe Li dendrite growth.This well-designed artificial SEI endows the Li metal with remarkable cycling stability over 550 cycles at a current density of 1 m A/cm^(2),significantly superior to the bare Li anode.Meanwhile,the full cell paired with a high-voltage LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)cathode delivers long-term stability with capacity retention(78%after 200 cycles)at 1 C and excellent rate performance.The findings highlight the importance of interface engineering in optimizing battery performance and longevity.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
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 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
基金the financial support from the National Natural Science Foundation of China(22408182)the Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(NJYT24024)the Natural Science Foundation of Inner Mongolia Autonomous Region(2023QN02007 and 2025QN02009)。
文摘Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmembrane cascade transport mechanism of biological ion pumps,we design a biomimetic dual-cascade separator(BDS)based on gradient pore core–shell Gd_(2)O_(3)@ZIF-7 nanoparticles to stabilize Li metal anodes.The mesoporous Gd_(2)O_(3)core,via Lewis acidic surface,weakens Li^(+) -solvent interactions,thereby reconstructing the solvation structure and achieving pre-desolvation.The microporous ZIF-7 shell then promotes final desolvation through strong confinement effect and N-rich site coordination,while its nanochannels homogenize Li^(+) transport.This synergistic meso/microporous gradient creates a unique dual-cascade effect for ion desolvation and transport.Consequently,BDS achieves a low desolvation energy barrier,a high Li^(+) transference number(0.71),and dendrite-free Li deposition.The average Coulombic efficiency rises from 72.7%to 98.4%,the cycling performance of the Li||Li symmetrical cell improves by 3.2 times,and the capacity retention of LiFePO_4(LFP)||Li full cell increases from 38.3%to73.4%after 500 cycles.This work offers a novel separator design concept,deepens Li deposition understanding,and guides separators from passive protection to active regulation.
基金financially supported by the Science and Technology Foundation of Henan Province(252102230017)the Doctoral Foundation of Henan University of Technology(2019BS005)+2 种基金the Talent Research Start-up Fund Project of Tongling University(2021tlxyrc23)the Natural Science Research Project of the Anhui Educational Committee(2023AH040234)the Scientific Research Projects of Tongling University(2022tlxyszZD04)。
文摘The development of aqueous zinc batteries(AZBs)is severely constrained by uncontrolled dendrite growth and parasitic interfacial reactions.Conventional solvation-dominated additives can mitigate these issues by altering the Zn^(2+)solvation structure,but they often compromise ion transport.Here,we introduce a molecular design principle for a non-solvating additive(NSA)based on inductive effects.Ethyl trifluoroacetate(ETFA),obtained by introducing an electron-withdrawing–CF_(3) group adjacent to the–C=O moiety of ethyl acetate(EA),participates minimally in the solvation structure but preferentially undergoes Gibbs adsorption at the Zn-electrolyte interface.This process reduces interfacial tension,reconstructs the electrical double layer,and orients ETFA molecules such that the hydrophilic–C=O groups face the electrolyte,modulating hydrogen-bonding networks,while the hydrophobic–CF_(3) groups anchor onto Zn to regulate deposition.As a result,dendrite formation and side reactions are simultaneously suppressed.With only 1 vol%ETFA,Zn-Cu cells achieve over 4000 stable cycles with 99.89%Coulombic efficiency.Zn-I_(2) full cells employing the modified electrolyte maintain stable operation for more than 500 cycles(6.8 mg cm^(-2),10μm Zn,N/P=2.86),and 0.3 Ah Zn-I_(2) pouch cells(30 mg cm^(-2),100μm Zn)can cycle stably for over 200 cycles.These findings highlight the critical role of Gibbs adsorption in interfacial regulation and provide insights for the molecular design of high-performance additives for stable Zn anodes.
基金supported by the National Research Foundation of Korea(NRF)grants funded by the Korean government(MSIT)(RS-2024-00409952,RS-2024-00347936,and RS-202400407282)supported by the GRRC Program of Gyeonggi Province(GRRCHanyang2020-B01)supported by the Commercialization Promotion Agency for R&D Outcomes(COMPA)grant funded by the Korean Government(MSIT)(RS-2023-00304763)。
文摘The practical use of lithium metal anodes(LMAs)is impeded by uncontrolled dendrite growth,primarily caused by uneven Li-ion flux and significant volume changes during cycling.To overcome these challenges,we present binder-free holey wrinkled-multilayered graphene(HWMG)scaffolds for highperformance LMAs with long cycle life.Holey graphene oxide(HGO)sheets were restacked into particle-like holey wrinkled-multilayered graphene oxide(HWMGO)in a high-concentration GO suspension,in which few-layer HGOs were quickly stabilized and wrinkled during the drying process,and upon reduction,they transformed into HWMG.HWMG exhibited excellent adhesion due to chemical interactions via edge-located functional groups.Its particle-like morphology,with numerous nanopores and high porosity,conferred outstanding mechanical flexibility and low tortuosity,enabling uniform Li-ion flux,buffering volume expansion,and suppressing dendrite growth.As a result,excellent long-term stability over 800 cycles and a voltage hysteresis of ca.7 mV over 6000 h were realized for the HWMG scaffolds,and a high areal capacity of 3.34 mAh cm^(-2) at 0.3 C after 350 cycles was demonstrated in a full-cell configuration.This work promotes the practical application of LMAs by offering a scalable scaffold design that suppresses dendrites and enhances cycle life.
基金supported by the National Natural Science Foundation of China(No.22179093 and 21905202)。
文摘Aqueous zinc-ion batteries(AZIBs)are considered promising for safe,low-cost,and sustainable energy storage.However,their practical deployment is critically hindered by dendrite formation and parasitic reactions at the Zn anode-electrolyte interface.To address this challenge,we present a self-assembly strategy to construct vertically aligned organic-inorganic hybrid nanosheet arrays composed of polyethyleneimine-zinc hydroxide sulfate(PEI-ZHS)via a simple coating-immersion method.The protonation of polyethyleneimine in ZnSO_(4) electrolyte provides localized alkaline conditions for controlled nucleation and growth of ZHS nanosheets at the anode interfa ce.This vertically aligned na noarchitectu re allows for fast Zn^(2+)transport and even nucleation by providing abundant oriented ion-conductive microchannels and accelerating desolvation.Benefiting from these characteristics,the PEI-ZHS layer effectively mitigates side reactions and dendrite growth.As a result,the modified zinc anodes achieve excellent cycling lifespans of 5200 and 1200 h at 1 mA cm^(-2)/1 mAh cm^(-2) and 5 mA cm^(-2)/5 mAh cm^(-2),respectively,in symmetric cells.The Zn‖I_(2) full cell also shows great reversibility,retaining 93.02%of initial capacity after 4000 cycles at 1 A g^(-1).This work introduces a thermodynamically guided and scalable interfacial engineering approach that advances the stability and performance of Zn metal anodes in AZIBs.
基金supported by the National Natural Science Foundation of China(32071715)the National Science Foundation of Tianjin City(22JCZDJC00560)。
文摘As an earth-abundant and natural biopolymer,cellulose has received significant attention in aqueous zinc-ion batteries(AZIBs)due to its inherent sustainability and non-toxicity,aligning perfectly with the core advantages of AZIBs.Nevertheless,the practical implementation of cellulose-based materials is limited by their intrinsically low ionic conductivity.Herein,we introduce a novel zincophilic artificial protective layer by strategically hybridizing hydroxypropyl cellulose(HPC)with zinc trifluoromethanesulfonate on a zinc metal anode(HZ@Zn).Characterization and calculations demonstrate that the multihydroxyl architecture of HPC constructs hydrogen bond networks,whereas the Zn^(2+)-coordinated HPC domains function as preferential nucleation sites for zinc deposition.These interactions collectively enhance ion transport and accelerate desolvation kinetics.Additionally,the hybrid layer's mechanical flexibility and interfacial adhesion ensure the integrity of the artificial protective layer during long cycling.Thanks to this synergistic effect,HZ@Zn shows exceptional electrochemical performance,including a low desolvation activation energy of 14.38 kJ mol^(-1)and ultra-long cycling stability.Symmetric cells demonstrate exceptional longevity,exceeding 9,500 h at 0.5 mA cm^(-2)/0.25 mAh cm^(-2),whereas HZ@Zn‖PANI full cells maintain 89.8%capacity retention after 4000 cycles at 5 A g^(-1).This study establishes biopolymers as versatile platforms for effectively stabilizing the zinc metal anode.
基金supported by the Basic Science Research Program(RS-2024-00455177)through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT.
文摘Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.
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financial support from the National Natural Science Foundation of China(NSFC No.52202253,ter for Microscopy and Analysis at the Nanjing University of Aero52372193,52472211,22293041)the Natural Science Foundation of Jiangsu Province(No.BK20220914)the Large Instrument and Equipment Sharing Fund of NUAA。
文摘A fatal issue of Zn-based electrochemical energy storage is uneven Zn^(2+)deposition on the Zn metal anode.Unfortunately,the modulation for the inherent electric field,the origin of driving force for ion diffusion,has been given insufficient importance.Herein,the redistribution of the surrounding electric field is demonstrated to depend on the permittivity of the surface medium for the first time,where highpermittivity particles can simultaneously enhance vertical components and reduce horizontal components of the electric field through polarization.Consequently,a bacterial cellulose-based separator is proposed by incorporating a high-permittivity surface medium.Cellulose serves as a robust substrate with a rather low thickness to enable homogeneous dispersion of high-permittivity particles on the surface,which can regulate the localized electric field to guide even Zn deposition by inhibiting twodimensional(2D)Zn^(2+)diffusion and suppressing side reactions by repulsing anion migration toward the Zn anode.The separator achieves significantly enhanced Zn anode stability of 2880 h at 1 mA cm^(-2)and a cumulative capacity of 3.5 Ah cm^(-2)at 10 mA cm^(-2).It also enables a long-term lifespan of 50,000 cycles in Zn||AC capacitor and 1000 cycles at a limited negative/positive(N/P)ratio of 3:1.This work provides a new view to stabilize Zn anode by electric field modulation.
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 National Natural Science Foundation of China(Nos.52372235,52073252,52002052,U20A20253,21972127,22279116)Key Scientific Research Project of Hangzhou(No.2024SZD1B12)+5 种基金Science and Technology Department of Zhejiang Province(Nos.2023C01231,Q23E020046,LD22E020006LY21E020005)Key Research and Development Project of Science and Technology Department of Sichuan Province(No.2022YFSY0004)Natural Science Foundation of Zhejiang Province(No.LQ23E020009)Sichuan Natural Science(No.2024NSFSC0951)Key Laboratory of Engineering Dielectrics and Its Application(Harbin University of Science and Technology),Ministry of Education(No.KFM 202303)。
文摘The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research.However,the practical implementation of lithium metal anodes is impeded by challenges such as dendrite formation and the inherent instability of the native oxide layer.This study introduces a novel liquid-source plasma technique to create a high-quality solid electrolyte interphase(SEI)composed of LiBr and LiBO_(2).According to first-principal calculation,LiBO_(2)optimizes the electrochemical dynamics and LiBr improves Li diffusion at the interfaces,thus protecting the Li metal from severe Li dendrite growth.This well-designed artificial SEI endows the Li metal with remarkable cycling stability over 550 cycles at a current density of 1 m A/cm^(2),significantly superior to the bare Li anode.Meanwhile,the full cell paired with a high-voltage LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)cathode delivers long-term stability with capacity retention(78%after 200 cycles)at 1 C and excellent rate performance.The findings highlight the importance of interface engineering in optimizing battery performance and longevity.
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(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 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.
