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
Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous struct...Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous structure and intrinsic lithiophilic property.In this work,we introduce interface-engineered cellulose-based separators by converting intrinsic hydroxyl groups on cellulose nanofibers(CNFs)to nitrogen functionalities through a trace conducting polymer coating.Both experimental and theoretical results reveal that the nitrogen moieties disrupt the compact hydrogen bond network within hydroxyl cellulose,enabling multiple nitrogen-lithium interactions that enhance lithium ion transport.In addition to an extraordinary Li^(+)transference number of 0.86 and a high ionic conductivity of 1.1 mS cm^(-1),the nitrogen-functionalized CNF contributes to a uniform electric field and Li^(+)concentration distribution across the lithium metal surface.This facilitates the formation of a LiF-rich solid electrolyte interface and suppresses Li dendrite growth.Consequently,Li‖Li cells demonstrate stable plating/stripping cycles for approximately 3000 h at a current density of 1 mA cm^(-2) with a fixed capacity of 1 mAh cm^(-2),while maintaining a low overpotential of 15 mV.Our work provides valuable insights into the surface functionalization of natural biomass for advancing sustainable energy storage technologies.展开更多
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 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
The advancement of aqueous zinc metal batteries(ZMBs)is constrained by intrinsic interfacial issues in aqueous electrolyte systems.Here,using numerical simulation,we decipher the multi-scale causes of interfacial inst...The advancement of aqueous zinc metal batteries(ZMBs)is constrained by intrinsic interfacial issues in aqueous electrolyte systems.Here,using numerical simulation,we decipher the multi-scale causes of interfacial instability,elucidating the synergistic effect of macroscopic ineffective regions and microscopic passivation.Based on the analysis,we develop an electrolyte-triggered interphase construction strategy to resolve the interfacial failure.This strategy couples the in situ formation of hydrogel interphase on both the anode and cathode with the electrolyte filling process,thereby(1)facilitating contact between electrodes and the separator;(2)promoting anode reversibility through inducing a bilayer SEI that enhances Zn^(2+)desolvation kinetics and blocks electron tunneling;(3)ensuring long-term cathode cycling stability via restricting the irreversible dissolution of MnO_(2)and side-reactions.The resultant Zn metal anode exhibited a near-unity Coulombic efficiency(99.5%)for Zn plating/stripping at an extremely low current density of 0.1 mA cm^(-2)and the Zn/MnO_(2)full cell sustained 2000 full-duty-cycles with an exceptionally low decay rate of 0.0051%per-cycle.This work unlocks an alternative angle for promoting practical ZMB s toward more sustainable energy storage systems.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
A new method for corrosion protection of Al-based metal matrix composites (MMC) was developed using two-step process, which involves anodizing in H2SO4 solution and sealing in rare earth solution. Corrosion resistance...A new method for corrosion protection of Al-based metal matrix composites (MMC) was developed using two-step process, which involves anodizing in H2SO4 solution and sealing in rare earth solution. Corrosion resistance of the treated surface was evaluated with polarization curves. The results showed that the effect of the protection using rare earth sealing is equivalent to that using chromate sealing for Al6061/SiCp. The rare earth metal salt can be an alternative to the toxic chromate for sealing anodized Al MMC.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
Nickel was deposited by ac electrolysis deposition in the pores of the porous oxide film of Al produced by anodizing in phosphoric acid. Ultrafine rod-shaped Ni particles were formed in the pores. At the same time a f...Nickel was deposited by ac electrolysis deposition in the pores of the porous oxide film of Al produced by anodizing in phosphoric acid. Ultrafine rod-shaped Ni particles were formed in the pores. At the same time a film of Ni oxide precursor was developed on the surface of the porous oxide film. The Ni particles and the Ni oxide precursor were examined by SEM, TEM and X-ray diffraction. The thickness of the barrier layer of the porous oxide film was thin and it attributed to the formation of the metal particles, while the formation of the oxide precursor was associated with the surface pits which were developed in the pretreatment of Al.展开更多
Li metal is widely recognized as the desired anode for next-generation energy storage,Li metal batteries,due to its highest theoretical capacity and lowest potential.Nonetheless,it suffers from unstable electrochemica...Li metal is widely recognized as the desired anode for next-generation energy storage,Li metal batteries,due to its highest theoretical capacity and lowest potential.Nonetheless,it suffers from unstable electrochemical behaviors like dendrite growth and side reactions in practical application.Herein,we report a highly stable anode with collector,Li_(5)Mg@Cu,realized by the melting-rolling process.The Li_(5)Mg@Cu anode delivers ultrahigh cycle stability for 2000 and 1000 h at the current densities of 1 and 2 mA cm^(-2),respectively in symmetric cells.Meanwhile,the Li_(5)Mg@Cu|LFP cell exhibits a high-capacity retention of 91.8% for 1000 cycles and 78.8% for 2000 cycles at 1 C.Moreover,we investigate the suppression effects of Mg on the dendrite growth by studying the performance of Li_(x)Mg@Cu electrodes with different Mg contents(2.0-16.7 at%).The exchange current density,surface energy,Li^(+)diffusion coefficient,and chemical stability of Li_(x)Mg@Cu concretely reveal this improving suppression effect when Mg content becomes higher.In addition,a Mg-rich phase with“hollow brick”morphology forming in the high Mg content Li_(x)Mg@Cu guides the uniform deposition of Li.This study reveals the suppression effects of Mg on Li dendrites growth and offers a perspective for finding the optimal component of Li-Mg alloys.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
Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven ...Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven distributions of the electric fields and ionic concentrations,forming“hot spots.”Hot spots may cause uncontrollable Li dendrites growth,presenting significant challenges to the cycle stability and safety of LMBs.To address these issues,we construct a Li ionic conductive-dielectric gradient bifunctional interlayer(ICDL)onto a 3D Li-injected graphene/carbon nanotube scaffold(LGCF)via in situ reaction of exfoliated hexagonal boron nitride(fhBN)and molten Li.Microscopic and spectroscopic analyses reveal that ICDL consists of fhBN-rich outer layer and inner layer enriched with Li_(3)N and Li-boron composites(Li-B).The outer layer utilizes dielectric properties to effectively homogenize the electric field,while the inner layer ensures high Li ion conductivity.Moreover,DFT calculations indicate that ICDL can effectively adsorb Li and decrease the Li diffusion barrier,promoting enhanced Li ion transport.The modulation of Li kinetics by ICDL increases the critical length of the Li nucleus,enabling suppression of Li dendrite growth.Attributing to these advantages,the ICDL-coated LGCF(ICDL@LGCF)demonstrates impressive long-term cycle performances in both symmetric cells and full cells.展开更多
Lithium metal anodes,with a theoretical capacity of up to 3860 mAh·g−1,are regarded as the cornerstone for developing next-generation high-energy-density batteries.However,several key challenges hinder their prac...Lithium metal anodes,with a theoretical capacity of up to 3860 mAh·g−1,are regarded as the cornerstone for developing next-generation high-energy-density batteries.However,several key challenges hinder their practical applications,includ-ing dendrite formation,unstable solid electrolyte interphase(SEI),side reactions with electrolytes,and associated safety risks.This review systematically explores the mechanisms of lithium nucleation,growth,and stripping in both liquid and solid-state battery systems,analyzing critical theoretical concepts like heterogeneous nucleation thermodynamics,surface diffusion kinetics,space charge effects,and SEI-induced nucleation,which are crucial for understanding the genesis of dendrite growth.Additionally,the review discusses the electrochemical-mechanical coupling failures that lead to SEI degra-dation and the formation of dead lithium.For liquid systems,the review proposes strategies to mitigate dendrite formation and SEI instability,which include electrolyte optimization,artificial SEI design,and electrode framework design.In solid-state batteries,the review offers a granular analysis of the interface challenges associated with polymer,sulfide,and halide electrolytes and summarizes different solutions for different solid-state electrolytes.Meanwhile,the review emphasizes the importance of advanced characterization techniques and computational modeling in understanding and regulating the interface between lithium metal and electrolytes.Looking ahead,the review highlights future research directions that emp-hasize the integration of cross-disciplinary approaches to tackle these interconnected challenges.By addressing these issues,the path will be clear for the rapid commercialization and widespread application of lithium metal batteries,bringing us closer to realizing stable,high-energy-density batteries that can satisfy the escalating demands of modern energy storage applications across various industries.展开更多
Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aq...Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aqueous electrolytes.A zincophilic carbon(ZC)layer was deposited on a Zn metal foil at 450°C by the up-stream pyrolysis of a hydrogen-bonded supramolecular substance framework,as-sembled from melamine(ME)and cyanuric acid(CA).The zincophilic groups(C=O and C=N)in the ZC layer guide uniform zinc plating/stripping and eliminate dendrites and side reactions.so that assembled symmetrical batteries(ZC@Zn//ZC@Zn)have a long-term service life of 2500 h at 1 mA cm^(−2) and 1 mAh cm^(−2),which is much longer than that of bare Zn anodes(180 h).In addition,ZC@Zn//V2O5 full batteries have a higher capacity of 174 mAh g^(−1) after 1200 cycles at 2 A g^(−1) than a Zn//V_(2)O_(5) counterpart(100 mAh g^(−1)).The strategy developed for the low-temperat-ure deposition of the ZC layer is a new way to construct advanced zinc metal anodes for ZMBs.展开更多
Severe lithium dendrite growth and elevated thermal runaway risks pose significant hurdles for fast-charging lithium metal batteries(LMBs)This study reports a polydopamine-functionalized hydroxyapatite/aramid(PDA@HA)h...Severe lithium dendrite growth and elevated thermal runaway risks pose significant hurdles for fast-charging lithium metal batteries(LMBs)This study reports a polydopamine-functionalized hydroxyapatite/aramid(PDA@HA)hybrid nanofibers separator to synchronously improve th fast-charging LMB's stability and safety.(1)The separator's surface,enriched with lithiophilic carbonyl and hydroxyl groups,accelerates Li~+ion desolvation,while electrophilic imine groups impede anion movement.This dual mechanism optimizes the Li^(+)-ion flux distribution on th anode,mitigating dendrite formation.(2)The polar PDA modification layer fosters the development of a Li_(3)N/LiF-rich solid electrolyt interface,further enhancing Li anode stability.Consequently,Li//Li symmetric cells with PDA@HA separators exhibit extended cycle life in L plating/stripping tests:5000 h at 1 mA cm^(-2)and 700 h at 20 mA cm^(-2),respectively,outperforming PP separators(80 h and 8 h).In LiFePO_(4)(LFP,^(2.1)mg cm^(-2))//Li full cell evaluation,the PDA@HA separator enables stable operation for 11,000 cycles at 18.2C with 87%capacity retention,significantly outperforming existing fast-charging LMB counterparts in literature.At a high LFP loading of 15.5 mg cm^(-2),the cel maintains 137.6 mAh g^(-1)(2.13 mAh cm^(-2))over 250 cycles at 3C,achieving 98%capacity retention.Moreover,the PDA@HA separato increases threshold temperature for thermal runaway and reduces the exothermic rate,intensifying the battery's thermal safety.This research underscores the importance of functional separator design in improving Li metal anode reversibility,fast-charging performance,and therma safety of LMBs.展开更多
Lithium (Li) metal batteries (LMBs) featuring ultrahigh energy densities are expected as ones of the mostprominent devices for future energy storage applications. Nevertheless, the practical application of LMBs is sti...Lithium (Li) metal batteries (LMBs) featuring ultrahigh energy densities are expected as ones of the mostprominent devices for future energy storage applications. Nevertheless, the practical application of LMBs is stillplagued by the poor interfacial stability of Li metal anode. Inorganic-rich interlayer derived from anion decom-positionin advanced liquid electrolytes is demonstrated as an efficient approach to stabilize the Li metal anode,however, is electrolyte-dependent with limited application conditions due to inappropriate electrolyte properties.Herein, an efficient structuration strategy is proposed to fabricate an electrolyte-independent and sustainedinorganic-rich layer, by embedding a type of functional anion aggregates consisting of selected anions ionicallybonded to polymerized cation clusters. The anion aggregates can progressively release anions to react with Liþand form key components boosting the structural stability and Liþ transfer ability of the artificial layer uponcycling. This self-reinforcing working mechanism endows the artificial layer with a sustained inorganic-richnature and promising Li protective ability during long-term cycling, while the electrolyte-independent propertyenables its applications in LMBs using conventional low concentration electrolytes and all-solid-state LMBs withsignificantly enhanced performances. This strategy establishes an alternative designing route of Li protectivelayers for reliable LMBs.展开更多
Gel polymer electrolytes(GPEs)present the best compromise between mechanical and electrochemical properties,as well as an improvement of the cell safety in the framework of Li metal batteries production.However,the po...Gel polymer electrolytes(GPEs)present the best compromise between mechanical and electrochemical properties,as well as an improvement of the cell safety in the framework of Li metal batteries production.However,the polymerization mechanism typically employed relies on the presence of an initiator,and is hindered by oxygen,thus impeding the industrial scale-up of the GPEs production.In this work,an UV-mediated thiol-ene polymerization,employing polyethylene glycol diacrylate(PEGDA)as oligomer,was carried out in a liquid electrolyte solution(1M LiTFSI in EC/DEC)to obtain a self-standing GPE.A comparative study between two different thiol-containing crosslinkers(trimethylolpropane tris(3-mercaptopropionate)-T3 and pentaerythritol tetrakis(3-mercaptopropionate)-T4)was carried out,studying the effects of the crosslinking environment and the GPE production methods on the cell performances.All the produced GPEs present an excellent room temperature ionic conductivity above 1 mS cm^(-1),as well as a wide electrochemical stability window up to 4.59 V.When cycled at a current density of C/10 for more than 250 cycles,all of the tested cells showed a stable cycling profile and a specific capacity>100 mAh g^(-1),indicating the suitability of such processes for up-scaling.展开更多
The electrochemical instability of traditional ether-based electrolytes poses a challenge for their use in high-voltage lithium metal batteries.Herein,a synergetic optimization strategy was proposed by introducing an ...The electrochemical instability of traditional ether-based electrolytes poses a challenge for their use in high-voltage lithium metal batteries.Herein,a synergetic optimization strategy was proposed by introducing an additive with a strong electron-withdrawing group and significant steric hindrance-isosorbide dinitrate(ISDN),reconstructing the solvation structure and solid electrolyte interphase(SEI),enabling highly stable and efficient lithium metal batteries.We found that ISDN can strengthen the interaction between Li^(+)and the anions of lithium salts and weaken the interaction between Li^(+)and the solvent in the solvation structure.It promotes the formation of a LiF-rich and LiN_(x)O_(y)-rich SEI layer,enhancing the uniformity and compactness of Li deposition and inhibiting solvent decomposition,which effectively expands the electrochemical window to 4.8 V.The optimized Li‖Li cells offer stable cycling over 1000 h with an overpotential of only 57.7 mV at 1 mA cm^(-2).Significantly,Li‖3.7 mA h LiFePO_(4)cells retain 108.3%of initial capacity after 546 cycles at a rate of 3 C.Under high-loading conditions(Li‖4.9 mA h LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)full cells)and a cutoff voltage of 4.5 V,the ISDN-containing electrolyte enables stable cycling for 140 cycles.This study leverages steric hindrance and electron-withdrawing effect to synergistically reconstruct the Li^(+)solvation structure and promote stable SEI formation,establishing a novel electrolyte paradigm for high-energy lithium metal batteries.展开更多
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 Natural Science Foundation of China(Grant No.22479046,22461142135)。
文摘Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous structure and intrinsic lithiophilic property.In this work,we introduce interface-engineered cellulose-based separators by converting intrinsic hydroxyl groups on cellulose nanofibers(CNFs)to nitrogen functionalities through a trace conducting polymer coating.Both experimental and theoretical results reveal that the nitrogen moieties disrupt the compact hydrogen bond network within hydroxyl cellulose,enabling multiple nitrogen-lithium interactions that enhance lithium ion transport.In addition to an extraordinary Li^(+)transference number of 0.86 and a high ionic conductivity of 1.1 mS cm^(-1),the nitrogen-functionalized CNF contributes to a uniform electric field and Li^(+)concentration distribution across the lithium metal surface.This facilitates the formation of a LiF-rich solid electrolyte interface and suppresses Li dendrite growth.Consequently,Li‖Li cells demonstrate stable plating/stripping cycles for approximately 3000 h at a current density of 1 mA cm^(-2) with a fixed capacity of 1 mAh cm^(-2),while maintaining a low overpotential of 15 mV.Our work provides valuable insights into the surface functionalization of natural biomass for advancing sustainable energy storage technologies.
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(62201369,52203142)Natural Science Foundation of Sichuan Province(2024NSFSC0226)the Open Fund of Key Laboratory of Green Chemical Technology of Fujian Province University(WYKF-EIGT2023-1)。
文摘The advancement of aqueous zinc metal batteries(ZMBs)is constrained by intrinsic interfacial issues in aqueous electrolyte systems.Here,using numerical simulation,we decipher the multi-scale causes of interfacial instability,elucidating the synergistic effect of macroscopic ineffective regions and microscopic passivation.Based on the analysis,we develop an electrolyte-triggered interphase construction strategy to resolve the interfacial failure.This strategy couples the in situ formation of hydrogel interphase on both the anode and cathode with the electrolyte filling process,thereby(1)facilitating contact between electrodes and the separator;(2)promoting anode reversibility through inducing a bilayer SEI that enhances Zn^(2+)desolvation kinetics and blocks electron tunneling;(3)ensuring long-term cathode cycling stability via restricting the irreversible dissolution of MnO_(2)and side-reactions.The resultant Zn metal anode exhibited a near-unity Coulombic efficiency(99.5%)for Zn plating/stripping at an extremely low current density of 0.1 mA cm^(-2)and the Zn/MnO_(2)full cell sustained 2000 full-duty-cycles with an exceptionally low decay rate of 0.0051%per-cycle.This work unlocks an alternative angle for promoting practical ZMB s toward more sustainable energy storage systems.
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.
文摘A new method for corrosion protection of Al-based metal matrix composites (MMC) was developed using two-step process, which involves anodizing in H2SO4 solution and sealing in rare earth solution. Corrosion resistance of the treated surface was evaluated with polarization curves. The results showed that the effect of the protection using rare earth sealing is equivalent to that using chromate sealing for Al6061/SiCp. The rare earth metal salt can be an alternative to the toxic chromate for sealing anodized Al MMC.
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National Natural Science Foundation of China!No. 59774031
文摘Nickel was deposited by ac electrolysis deposition in the pores of the porous oxide film of Al produced by anodizing in phosphoric acid. Ultrafine rod-shaped Ni particles were formed in the pores. At the same time a film of Ni oxide precursor was developed on the surface of the porous oxide film. The Ni particles and the Ni oxide precursor were examined by SEM, TEM and X-ray diffraction. The thickness of the barrier layer of the porous oxide film was thin and it attributed to the formation of the metal particles, while the formation of the oxide precursor was associated with the surface pits which were developed in the pretreatment of Al.
基金supported by the Qingdao Jiuhuanxinyue New Energy Technology Co.,Ltd.the Guangdong Basic and Applied Basic Research Foundation(Grant No.2021B1515120071)+2 种基金the 21C Innovation Laboratory,Contemporary Amperex Technology Ltd.(Grant No.21C-OP-202112)the financial support from the Guangdong Basic and Applied Basic Research Foundation(Grant No.2024A1515011873)the Shenzhen Science and Technology Program(Grant No.JCYJ20220531095212027).
文摘Li metal is widely recognized as the desired anode for next-generation energy storage,Li metal batteries,due to its highest theoretical capacity and lowest potential.Nonetheless,it suffers from unstable electrochemical behaviors like dendrite growth and side reactions in practical application.Herein,we report a highly stable anode with collector,Li_(5)Mg@Cu,realized by the melting-rolling process.The Li_(5)Mg@Cu anode delivers ultrahigh cycle stability for 2000 and 1000 h at the current densities of 1 and 2 mA cm^(-2),respectively in symmetric cells.Meanwhile,the Li_(5)Mg@Cu|LFP cell exhibits a high-capacity retention of 91.8% for 1000 cycles and 78.8% for 2000 cycles at 1 C.Moreover,we investigate the suppression effects of Mg on the dendrite growth by studying the performance of Li_(x)Mg@Cu electrodes with different Mg contents(2.0-16.7 at%).The exchange current density,surface energy,Li^(+)diffusion coefficient,and chemical stability of Li_(x)Mg@Cu concretely reveal this improving suppression effect when Mg content becomes higher.In addition,a Mg-rich phase with“hollow brick”morphology forming in the high Mg content Li_(x)Mg@Cu guides the uniform deposition of Li.This study reveals the suppression effects of Mg on Li dendrites growth and offers a perspective for finding the optimal component of Li-Mg alloys.
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the financial support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2023R1A2C2007699 and 2022R1A6A1A0306303912)the Nano Material Technology Development Program through the NRF funded by the Ministry of Science and ICT (NRF-2015M3A7B6027970)the Technology Innovation Program by the Ministry of Trade, Industry & Energy (RS-202300236794)
文摘Regulating lithium(Li)plating/stripping behavior in three-dimensional(3D)conductive scaffolds is critical to stabilizing Li metal batteries(LMBs).Surface protrusions and roughness in these scaffolds can induce uneven distributions of the electric fields and ionic concentrations,forming“hot spots.”Hot spots may cause uncontrollable Li dendrites growth,presenting significant challenges to the cycle stability and safety of LMBs.To address these issues,we construct a Li ionic conductive-dielectric gradient bifunctional interlayer(ICDL)onto a 3D Li-injected graphene/carbon nanotube scaffold(LGCF)via in situ reaction of exfoliated hexagonal boron nitride(fhBN)and molten Li.Microscopic and spectroscopic analyses reveal that ICDL consists of fhBN-rich outer layer and inner layer enriched with Li_(3)N and Li-boron composites(Li-B).The outer layer utilizes dielectric properties to effectively homogenize the electric field,while the inner layer ensures high Li ion conductivity.Moreover,DFT calculations indicate that ICDL can effectively adsorb Li and decrease the Li diffusion barrier,promoting enhanced Li ion transport.The modulation of Li kinetics by ICDL increases the critical length of the Li nucleus,enabling suppression of Li dendrite growth.Attributing to these advantages,the ICDL-coated LGCF(ICDL@LGCF)demonstrates impressive long-term cycle performances in both symmetric cells and full cells.
基金supported by grants from the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant Nos.XDB1040100 and XDB1040300)the National Natural Science Foundation of China(Grant Nos.22379108,52202279,52225105,22279127,22425403,92372125,22421001,22205241,22425403,92372125,22421001,22205241,92472207,52472223,52102280,22393900 and 22209010)+1 种基金the National Key Research and Development Program of China(Grant Nos.2021YFF0500600 and 2021YFB2500300)the Fundamental Research Funds for the Central Univer-sities(Grant No.WK9990000170)。
文摘Lithium metal anodes,with a theoretical capacity of up to 3860 mAh·g−1,are regarded as the cornerstone for developing next-generation high-energy-density batteries.However,several key challenges hinder their practical applications,includ-ing dendrite formation,unstable solid electrolyte interphase(SEI),side reactions with electrolytes,and associated safety risks.This review systematically explores the mechanisms of lithium nucleation,growth,and stripping in both liquid and solid-state battery systems,analyzing critical theoretical concepts like heterogeneous nucleation thermodynamics,surface diffusion kinetics,space charge effects,and SEI-induced nucleation,which are crucial for understanding the genesis of dendrite growth.Additionally,the review discusses the electrochemical-mechanical coupling failures that lead to SEI degra-dation and the formation of dead lithium.For liquid systems,the review proposes strategies to mitigate dendrite formation and SEI instability,which include electrolyte optimization,artificial SEI design,and electrode framework design.In solid-state batteries,the review offers a granular analysis of the interface challenges associated with polymer,sulfide,and halide electrolytes and summarizes different solutions for different solid-state electrolytes.Meanwhile,the review emphasizes the importance of advanced characterization techniques and computational modeling in understanding and regulating the interface between lithium metal and electrolytes.Looking ahead,the review highlights future research directions that emp-hasize the integration of cross-disciplinary approaches to tackle these interconnected challenges.By addressing these issues,the path will be clear for the rapid commercialization and widespread application of lithium metal batteries,bringing us closer to realizing stable,high-energy-density batteries that can satisfy the escalating demands of modern energy storage applications across various industries.
基金partially supported by the National Natural Science Foundation of China(22479022)Liaoning Revitalization Talents Program(XLYC2007129)。
文摘Aqueous zinc metal batteries(ZMBs)which are environmentally benign and cheap can be used for grid-scale energy storage,but have a short cycling life mainly due to the poor reversibility of zinc metal anodes in mild aqueous electrolytes.A zincophilic carbon(ZC)layer was deposited on a Zn metal foil at 450°C by the up-stream pyrolysis of a hydrogen-bonded supramolecular substance framework,as-sembled from melamine(ME)and cyanuric acid(CA).The zincophilic groups(C=O and C=N)in the ZC layer guide uniform zinc plating/stripping and eliminate dendrites and side reactions.so that assembled symmetrical batteries(ZC@Zn//ZC@Zn)have a long-term service life of 2500 h at 1 mA cm^(−2) and 1 mAh cm^(−2),which is much longer than that of bare Zn anodes(180 h).In addition,ZC@Zn//V2O5 full batteries have a higher capacity of 174 mAh g^(−1) after 1200 cycles at 2 A g^(−1) than a Zn//V_(2)O_(5) counterpart(100 mAh g^(−1)).The strategy developed for the low-temperat-ure deposition of the ZC layer is a new way to construct advanced zinc metal anodes for ZMBs.
基金supported by the National Natural Science Foundation of China(Grant No.52202328,52372099,52271222)the Shanghai Sailing Program(22YF1455500)。
文摘Severe lithium dendrite growth and elevated thermal runaway risks pose significant hurdles for fast-charging lithium metal batteries(LMBs)This study reports a polydopamine-functionalized hydroxyapatite/aramid(PDA@HA)hybrid nanofibers separator to synchronously improve th fast-charging LMB's stability and safety.(1)The separator's surface,enriched with lithiophilic carbonyl and hydroxyl groups,accelerates Li~+ion desolvation,while electrophilic imine groups impede anion movement.This dual mechanism optimizes the Li^(+)-ion flux distribution on th anode,mitigating dendrite formation.(2)The polar PDA modification layer fosters the development of a Li_(3)N/LiF-rich solid electrolyt interface,further enhancing Li anode stability.Consequently,Li//Li symmetric cells with PDA@HA separators exhibit extended cycle life in L plating/stripping tests:5000 h at 1 mA cm^(-2)and 700 h at 20 mA cm^(-2),respectively,outperforming PP separators(80 h and 8 h).In LiFePO_(4)(LFP,^(2.1)mg cm^(-2))//Li full cell evaluation,the PDA@HA separator enables stable operation for 11,000 cycles at 18.2C with 87%capacity retention,significantly outperforming existing fast-charging LMB counterparts in literature.At a high LFP loading of 15.5 mg cm^(-2),the cel maintains 137.6 mAh g^(-1)(2.13 mAh cm^(-2))over 250 cycles at 3C,achieving 98%capacity retention.Moreover,the PDA@HA separato increases threshold temperature for thermal runaway and reduces the exothermic rate,intensifying the battery's thermal safety.This research underscores the importance of functional separator design in improving Li metal anode reversibility,fast-charging performance,and therma safety of LMBs.
基金supported by the Research Fund of Jianghan Univer-sity(2024JCYJ02)the Graduate Scientific Research Foundation of Jianghan University(KYCXJJ202428)+1 种基金the Excellent Discipline Cultiva-tion Project funded by Jianghan University(2023XKZ013)the Na-tional Natural Science Foundation of China(Grant No.22179052).
文摘Lithium (Li) metal batteries (LMBs) featuring ultrahigh energy densities are expected as ones of the mostprominent devices for future energy storage applications. Nevertheless, the practical application of LMBs is stillplagued by the poor interfacial stability of Li metal anode. Inorganic-rich interlayer derived from anion decom-positionin advanced liquid electrolytes is demonstrated as an efficient approach to stabilize the Li metal anode,however, is electrolyte-dependent with limited application conditions due to inappropriate electrolyte properties.Herein, an efficient structuration strategy is proposed to fabricate an electrolyte-independent and sustainedinorganic-rich layer, by embedding a type of functional anion aggregates consisting of selected anions ionicallybonded to polymerized cation clusters. The anion aggregates can progressively release anions to react with Liþand form key components boosting the structural stability and Liþ transfer ability of the artificial layer uponcycling. This self-reinforcing working mechanism endows the artificial layer with a sustained inorganic-richnature and promising Li protective ability during long-term cycling, while the electrolyte-independent propertyenables its applications in LMBs using conventional low concentration electrolytes and all-solid-state LMBs withsignificantly enhanced performances. This strategy establishes an alternative designing route of Li protectivelayers for reliable LMBs.
基金the project PNRR-NGEU,which has received funding from the MUR-DM 352/2022.
文摘Gel polymer electrolytes(GPEs)present the best compromise between mechanical and electrochemical properties,as well as an improvement of the cell safety in the framework of Li metal batteries production.However,the polymerization mechanism typically employed relies on the presence of an initiator,and is hindered by oxygen,thus impeding the industrial scale-up of the GPEs production.In this work,an UV-mediated thiol-ene polymerization,employing polyethylene glycol diacrylate(PEGDA)as oligomer,was carried out in a liquid electrolyte solution(1M LiTFSI in EC/DEC)to obtain a self-standing GPE.A comparative study between two different thiol-containing crosslinkers(trimethylolpropane tris(3-mercaptopropionate)-T3 and pentaerythritol tetrakis(3-mercaptopropionate)-T4)was carried out,studying the effects of the crosslinking environment and the GPE production methods on the cell performances.All the produced GPEs present an excellent room temperature ionic conductivity above 1 mS cm^(-1),as well as a wide electrochemical stability window up to 4.59 V.When cycled at a current density of C/10 for more than 250 cycles,all of the tested cells showed a stable cycling profile and a specific capacity>100 mAh g^(-1),indicating the suitability of such processes for up-scaling.
基金Recruitment Program of Global Experts(China)the Hundred-Talent Project of Fujian+1 种基金Fuzhou UniversityFuda Zijin Hydrogen Energy Technology Co.,Ltd for the financial support。
文摘The electrochemical instability of traditional ether-based electrolytes poses a challenge for their use in high-voltage lithium metal batteries.Herein,a synergetic optimization strategy was proposed by introducing an additive with a strong electron-withdrawing group and significant steric hindrance-isosorbide dinitrate(ISDN),reconstructing the solvation structure and solid electrolyte interphase(SEI),enabling highly stable and efficient lithium metal batteries.We found that ISDN can strengthen the interaction between Li^(+)and the anions of lithium salts and weaken the interaction between Li^(+)and the solvent in the solvation structure.It promotes the formation of a LiF-rich and LiN_(x)O_(y)-rich SEI layer,enhancing the uniformity and compactness of Li deposition and inhibiting solvent decomposition,which effectively expands the electrochemical window to 4.8 V.The optimized Li‖Li cells offer stable cycling over 1000 h with an overpotential of only 57.7 mV at 1 mA cm^(-2).Significantly,Li‖3.7 mA h LiFePO_(4)cells retain 108.3%of initial capacity after 546 cycles at a rate of 3 C.Under high-loading conditions(Li‖4.9 mA h LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)full cells)and a cutoff voltage of 4.5 V,the ISDN-containing electrolyte enables stable cycling for 140 cycles.This study leverages steric hindrance and electron-withdrawing effect to synergistically reconstruct the Li^(+)solvation structure and promote stable SEI formation,establishing a novel electrolyte paradigm for high-energy lithium metal batteries.
