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
The deployment of safe and high-energy density lithium metal polymer batteries(LMPBs)still requires further advances in the quest for new solid polymer electrolytes(SPEs).In this regard,salt anions have a decisive rol...The deployment of safe and high-energy density lithium metal polymer batteries(LMPBs)still requires further advances in the quest for new solid polymer electrolytes(SPEs).In this regard,salt anions have a decisive role in the overall SPE performance.While lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)was chosen earlier to have a highly flexible sulfonimide center and an extensively delocalized negative charge,it still suffers from several drawbacks ascribed to its poor interfacial compatibility with the lithium metal(LiM)anode and the fact that it is a PFAS.In this work,a novel lithium salt is cunningly designed,aiming to combine the advantages of previously reported lithium bis(fluorosulfonyl)imide(LiFSI)and lithium bis(difluoromethanesulfonyl)imide(LiDFSI)to overcome the limitations of the state-of-the-art SPE based on LiTFSI/poly(ethylene oxide)(PEO).The SPE containing the developed(difluoromethanesulfonyl)(fluorosulfonyl)imide(LiDFFSI)salt presented reduced interfacial resistance and improved compatibility with the lithium metal(LiM)anode compared with LiTFSI/PEO,enabled by the formation of a stable,uniform,and ionically conductive solid–electrolyte interphase(SEI).In addition,LiDFFSI-based SPEs demonstrated a prolonged cycling stability,achieving over 125 cycles at C/10 with minimal capacity fading in LiM||LiFePO_(4) cell configuration.These findings evidence how a rational design of the lithium salt chemistry allows tuning the formed SEI,directly impacting the overall SPE performance.Thus,LiDFFSI is presented as a promising alternative lithium salt to improve electrochemical performance and interfacial stability in next-generation LiM batteries.展开更多
Interfacial engineering,particularly the design of artificial solid-electrolyte interphases(SEIs),has been successfully applied in all-solid-state batteries(ASSLBs)for industrial applications.However,a fundamental und...Interfacial engineering,particularly the design of artificial solid-electrolyte interphases(SEIs),has been successfully applied in all-solid-state batteries(ASSLBs)for industrial applications.However,a fundamental understanding of the synthesis and mechanism models of artificial SEIs in all-solid-state Li-ion batteries remains limited.In this review,recent advances in designing and synthesizing artificial SEIs for ASSLBs to solve interfacial issues are thoroughly discussed,covering three main preparation methods and their technical routes:1)atomic layer deposition,2)sol-gel methods,and 3)mechanical ball-milling methods.Moreover,advanced ex-situ characterization techniques for artificial SEIs are comprehensively summarized.Finally,this review provides perspectives on techniques for the interface engineering of artificial SEIs for ASSLBs,with focus on promising methods for industrial applications.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
Aqueous rechargeable zinc ion batteries have received widespread attention due to their high energy density and low cost.However,zinc metal anodes face fatal dendrite growth and detrimental side reactions,which affect...Aqueous rechargeable zinc ion batteries have received widespread attention due to their high energy density and low cost.However,zinc metal anodes face fatal dendrite growth and detrimental side reactions,which affect the cycle stability and practical application of zinc ion batteries.Here,an in-situ formed hierarchical solid-electrolyte interphase composed of InF3,In,and ZnF2 layers with outside-in orientation on the Zn anode(denoted as Zn@InF3)is developed by a sample InF3 coating.The inner ultrathin ZnF2 interface between Zn anode and InF3 layer formed by the spontaneous galvanic replacement reaction between InF3 and Zn,is conductive to achieving uniform Zn deposition and inhibits the growth of Zinc dendrites due to the high electrical resistivity and Zn2+conductivity.Meanwhile,the middle uniformly generated metallic In and outside InF3 layers functioning as corrosion inhibitor suppressing the side reaction due to the waterproof surfaces,good chemical inactivity,and high hydrogen evolution overpotential.Besides,the as-prepared zinc anode enables dendrite-free Zn plating/stripping for more than 6,000 h at nearly 100%coulombic efficiency(CE).Furthermore,coupled with the MnO2 cathode,the full battery exhibits the long cycle of up to 1,000 cycles with a low negative-to-positive electrode capacity(N/P)ratio of 2.8.展开更多
Sulfide-based solid-state electrolytes(SSEs)with high Li+conductivity(δLi^(+))and trifling grain boundaries have great potential for all-solid-state lithium-metal batteries(ASSLMBs).Nonetheless,the in-situ developmen...Sulfide-based solid-state electrolytes(SSEs)with high Li+conductivity(δLi^(+))and trifling grain boundaries have great potential for all-solid-state lithium-metal batteries(ASSLMBs).Nonetheless,the in-situ development of mixed ionic-electronic conducting solid-electrolyte interphase(SEI)at sulfide electrolyte/Li-metal anode interface induces uneven Li electrodeposition,which causes Li-dendrites and void formation,significantly severely deteriorating ASSLMBs.Herein,we propose a dual anionic,e.g.,F and N,doping strategy to Li7P3S11,tuning its composition in conjunction with the chemistry of SEI.Therefore,novel Li_(6.58)P_(2.76)N_(0.03)S_(10.12)F_(0.05)glass-ceramic electrolyte(Li_(7)P_(3)S_(11-5)LiF-3Li_(3)N-gce)achieved superior ionic(4.33 mS·cm^(−1))and lowest electronic conductivity of 4.33×10^(−10)S·cm^(−1)and thus,offered superior critical current density of 0.90 mA·cm^(−2)(2.5 times】Li7P3S11)at room temperature(RT).Notably,Li//Li cell with Li6.58P2.76N0.03S10.12F0.05-gce cycled stably over 1000 and 600 h at 0.2 and 0.3 mA·cm^(−2)credited to robust and highly conductive SEI(in-situ)enriched with LiF and Li3N species.Li3N’s wettability renders SEI to be highly Li+conductive,ensures an intimate interfacial contact,blocks reductive reactions,prevents Li-dendrites and facilitates fast Li+kinetics.Consequently,LiNi0.8Co0.15Al0.05O_(2)(NCA)/Li_(6.58)P_(2.76)N_(0.03)S_(10.12)F_(0.05)-gce/Li cell exhibited an outstanding first reversible capacity of 200.8/240.1 mAh·g^(−1)with 83.67%Coulombic efficiency,retained 85.11%of its original reversible capacity at 0.3 mA·cm^(−2)over 165 cycles at RT.展开更多
High-voltage Li-rich Mn-based oxide(LRMO)cathodes are promising for breaking through the energy density limits of lithium-ion batteries,yet their practical application remains limited by electrochemical performance de...High-voltage Li-rich Mn-based oxide(LRMO)cathodes are promising for breaking through the energy density limits of lithium-ion batteries,yet their practical application remains limited by electrochemical performance degradation caused by unstable cathode-electrolyte interphase(CEI)evolution during longterm cycling.To address this issue,we propose a novel surface modification strategy using La_(0.7)Sr_(0.3)MnO_(3-σ)(LSMO)nanodots,which exhibit high electronic co nductivity and excellent corrosion resistance.These nanodots act as stable anchoring sites,facilitating the formation of a robust CEI on LRMO,The LSMOmodified cathode demonstrates significantly improved anionic redox reversibility,effectively mitigating transition metal migration and lattice oxygen loss.Furthermore,the optimized interfacial electrochemical kinetics ensure sustained rapid Li+diffusion throughout cycling,while the formation of a stable trilayer CEI structure suppresses electrolyte decomposition.Benefiting from these synergistic effects,the LSMO nanodot-engineered LRMO cathode delivers outstanding cycling stability,retaining 97.4%capacity after 300 cycles at 1 C.This work not only highlights the critical role of nanodot heterostructures in stabilizing CEI but also provides a new approach to designing high-voltage cathodes with superior interfacial compatibility and long-term durability.展开更多
Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditio...Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditions)faces significant challenges,including accelerated electrolyte decomposition,interfacial instability,and potential thermal runaway risks.To address these challenges,we present a solvation-interphase synergistic regulation strategy using 2-fluorobenzenesulfonamide(2-FBS)as a multifunctional electrolyte additive.The 2-FBS molecule effectively modulates the Li^(+)solvation structure by reducing the coordination of ethylene carbonate(EC)solvent.This transformation suppresses EC-induced parasitic reactions while scavenging superoxide radicals,thereby mitigating gas evolution at electrode interfaces.Upon preferential decomposition,2-FBS further promotes the formation of a robust LiF-Li_(3)N-Li_(2)S-rich interphase with exceptional mechanical strength(Young’s modulus:39.4 GPa).This inorganic-rich hybrid interphase simultaneously enables dendrite-free lithium plating and enhances cathode thermal stability.Consequently,2-FBS-modified electrolyte empowers LiCoO_(2)//Li cells to deliver 82.8%capacity retention after 800 cycles at 55°C and sustain 81.2%capacity retention after 1500 cycles at 4 C.Moreover,practical validation through nail penetration tests confirms the effectiveness of the electrolyte in preventing thermal propagation in fully charged pouch cells.This work establishes a paradigm for enabling reliable battery operation under extreme conditions through synergistic solvation and interphase engineering.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
Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The ch...Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions.In this study,we have tuned orbital hybridization states forming an interface enriched with sp^(2) hybridized carbon(sp^(2)-C),which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation.Benefiting from successfully constructed inorganic-rich SEI,the ICE increased to 91%and sodium storage capacity reached 346 mAh/g.Besides,the capacity retention rate was 90.7%after 700 cycles at 1 A/g higher than pristine electrode(83.8%).展开更多
High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instab...High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.展开更多
The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electr...The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO_(2) battery by using trimethylsilyl isocyanate(TMIS)as electrolyte additive.The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI.By the synergistic action,the Co3+dissolution problem of the LiCoO_(2) cathode was effectively curbed.Furthermore,TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li^(+).As expected,the 4.6 V Li||LiCoO_(2) battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.展开更多
Weakly solvating electrolytes(WSEs)promote the formation of anion-driven solid electrolyte interphases(SEI),enabling stable lithium metal batteries.However,current strategies involving alkylated modification,steric hi...Weakly solvating electrolytes(WSEs)promote the formation of anion-driven solid electrolyte interphases(SEI),enabling stable lithium metal batteries.However,current strategies involving alkylated modification,steric hindrance incorporation,coordinated oxygen(O)regulation,and selective fluorination face poor-diversity interfacial chemistry,high cost,or environmental concerns.Here,we propose a heteroatom-substitution strategy to design a WSE composed of lithium bis(fluorosulfonyl)imide(LiFSI)and 1,4-oxathiane(OTA)as a single solvent.Substituting oxygen with sulfur in conventional 1,4-dioxane(1,4-DX)generates OTA with a modulated dipole and charge distribution,weakening Li^(+)-OTA coordination while promoting anion-involved solvation sheath.This unique solvation structure triggers the formation of an inorganic-rich SEI with sulfur-containing species,enabling high Li plating/stripping coulombic efficiency and stable Li‖Li symmetric cells cycling for 1000 h.Benefiting from the superior interfacial chemistry and wettability of the electrolyte to the LiFePO_(4) cathode,full cells exhibit exceptional cycling stability even at low negative-to-positive(N/P)ratios,A pouch cell coupled with3.58 mAh cm^(-2) LiFePO_(4) and 20μm Li(N/P~1.15)maintains 88.77%capacity after 150 cycles.This work shows a fluorine-free solvent design paradigm for advanced WSEs,providing novel insights toward stable LMBs.展开更多
Li_(7)La_(3)Zr_(2)O_(12)-based electrolytes have got great promise for solid-state lithium(Li)metal batteries because of their high elastic modulus and wide electrochemical stability window.However,the insufficient co...Li_(7)La_(3)Zr_(2)O_(12)-based electrolytes have got great promise for solid-state lithium(Li)metal batteries because of their high elastic modulus and wide electrochemical stability window.However,the insufficient contact and heterogeneous Li deposition severely hinder their practical applications.Here,a flexible ternary polymethacrylate(PMA)matrix is designed to incorporate with Ta-doped Li_(7)La_(3)Zr_(2)O_(12)(LLZTO-PMA).The PMA matrix ensures excellent interfacial contact,while the synergistic effects of its polar carbonyl groups and its interaction with LLZTO creating fast interfacial Li^(+)pathways yield a high ionic conductivity of 0.266 mS cm^(-1)at 20℃.Moreover,the interaction between LLZTO and PMA matrix further guides the formation of a hybrid LiF/Li_(3)N-rich solid electrolyte interphase,which allows a fast Li^(+)interfacial kinetic due to its lowered Li^(+)diffusion barrier.Consequently,the LLZTO-PMA electrolyte contributes an ultra-stable Li anode interphase,attaining a lifespan exceeding 10,000 h in symmetric cells and retaining over 96%capacity after 600 cycles in full battery,demonstrating a breakthrough for high-performance solid-state batteries.展开更多
Anode-free sodium metal batteries(AFSMBs)have gained attention as next-generation storage systems with high energy density and cost-effectiveness.However,non-uniform sodium(Na)deposition and an unsteady solid electrol...Anode-free sodium metal batteries(AFSMBs)have gained attention as next-generation storage systems with high energy density and cost-effectiveness.However,non-uniform sodium(Na)deposition and an unsteady solid electrolyte interphase(SEI)lead to dendrite-related issues and severe irreversible Na^(+)plating/stripping,greatly aggravating their cycle deterioration.In this study,we effectively modified the 3D current collector's electronic structure by introducing Zn-N_(x)active sites(Zn-CNF),which enhances lateral Na^(+)diffusion and the Na planar growth,enabling uniform deep Na deposition at an exceptionally high capacity of 10 mA h cm^(-2).Furthermore,the Zn-N_(x)bonds enhance the adsorption capacity of PF6and contribute to forming a stable inorganic-rich SEI layer.Consequently,Zn-CNF with the electronic structure regulation endows an ultra-low nucleation overpotential(8 mV)and ultra-high Coulombic efficiency of 99.94%over 1,600 cycles.Symmetric cells demonstrate stable Na^(+)plating/stripping behavior for more than 4,400 h at 1 mA cm^(-2).Moreover,under high cathode loading(7.97 mg cm^(-2)),the AFSMBs achieve a high energy density of 374 W h kg^(-1)and retain a high discharge capacity of 82.49 mA h g^(-1)with a capacity retention of 80.4%after 120 cycles.This work proposes a viable strategy to achieving high-energy-density AFSMBs.展开更多
The substantial influences of Mo contents varying from 0 to 0.26 and 0.50 wt.%on the microstructural evolution and MX(M=Nb,V and Mo;X=C and N)precipitation characteristics of Nb–V–N microalloyed steels processed by ...The substantial influences of Mo contents varying from 0 to 0.26 and 0.50 wt.%on the microstructural evolution and MX(M=Nb,V and Mo;X=C and N)precipitation characteristics of Nb–V–N microalloyed steels processed by hot deformation and continuous cooling were studied using a Gleeble 3800 thermomechanical simulator.Metallographic analysis showed that the ferrite microstructure transformed from polygonal ferrite(PF)in 0Mo steel to both acicular ferrite(AF)and PF in 0.26Mo and 0.50Mo steels,and AF content first increased and then decreased.The thermodynamic calculations and the experimental results proved that the quantity of solid solution of Mo in austenite obviously increased,which reduced the austenite(γ)to ferrite(α)transformation temperature,consequently promoting AF formation in 0.26Mo steel and bainite transformation in 0.50Mo steel.Moreover,the submicron Nb-rich MX particles that precipitated at the temperature of the austenite region further induced AF heterogeneous nucleation with an orientation relationship of(100)_(MX)//(100)_(Ferrite)and[■][001]Ferrite.The interphase precipitation of the nanosized V-rich MX particles with Mo partitioning that precipitated duringγ→αtransformation exhibited a Baker–Nutting orientation relationship of(100)_(MX)//(100)Ferrite and[001]_(MX)//[■]_(Ferrite)with respect to the ferrite matrix.With increasing Mo content from 0 to 0.26 and 0.50 wt.%,the sheet spacing decreased from 46.9–49.0 to 34.6–38.6 and 25.7–28.0 nm,respectively,which evidently hindered dislocation movement and greatly enhanced precipitation strengthening.Furthermore,facilitating AF formation and interphase precipitation was beneficial to improving steel properties,and the optimal Mo content was 0.26 wt.%.展开更多
Solid-state batteries have recently raised strong interest in the scientific community as possible advancement of battery technology beyond commercial lithium ion due to the promise of high energy densities and improv...Solid-state batteries have recently raised strong interest in the scientific community as possible advancement of battery technology beyond commercial lithium ion due to the promise of high energy densities and improved safety[1].In the core of development of high-performance solid-state batteries,is the development of solid-state electrolytes,which should be both sufficiently ionically conductive and offer stable interphases with high-energy electrodes,such as alkali metals and silicon[2,3].Recently,potassium-ion batteries have emerged as an alternative to lithium-ion batteries as a remedy to limited resources and uneven distribution of lithium,as well as due to the fact that low standard electrode potentials of K/K^(+) electrodes should lead to high operation voltages,competitive to those observed in commercial lithium batteries[4-6].展开更多
High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based ...High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based electrolytes,particularly at extreme temperatures.In this study,we develop a stable electrolyte incorporating lithium difluorophosphate(LiDFP)as an additive to enhance the electrochemical performance of DIBs over a wide temperature range.LiDFP preferentially decomposes to form a rapid anion-transporting,mechanically robust CEI layer on graphite,which provides better protection by suppressing graphite's volume expansion,preventing electrolyte oxidative decomposition,and enhancing reaction kinetics.As a result,Li||graphite half cells using LiDFP electrolyte exhibit outstanding rate performance(90.8% capacity retention at 30 C)and excellent cycle stability(82.2% capacity retention after 5000 cycles)at room temperature.Moreover,graphite||graphite full cells with LiDFP electrolyte demonstrate stable discharge capacity across a temperature range of-20 to 40℃,expanding the potential applications of LiDFP.This work establishes a novel strategy for optimizing the interphase through electrolyte design,paving the way for all-climate DIBs with improved performance and stability.展开更多
FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium stor...FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium storage.Rational structural design is one way to overcome these drawbacks.In this work,MIL-88B-Fe-derived FeS_(2)nanoparticles/N-doped carbon nanofibers(M-FeS_(2)@CNFs)with expansion buffer capability are designed and synthesized for high-performance PIB anodes via electrospinning and subsequent sulfurization.The uniformly distributed cavity-type porous structure effectively mitigates the severe aggregation problem of FeS_(2)nanoparticles during cycling and buffers the volume change,further enhancing the potassium storage capacity.Meanwhile,the robust KF-rich solid electrolyte interphase induced by methyl trifluoroethylene carbonate(FEMC)additive improves the cycling stability of the M-FeS_(2)@CNF anode.In the electrolyte with 3 wt%FEMC,the M-FeS_(2)@CNF anode shows a reversible specific capacity of 592.7 mA h g^(-1)at 0.1 A g^(-1),an excellent rate capability of 327.1 mA h g^(-1)at 5 A g^(-1),and a retention rate 80.7%over 1000 cycles at 1 A g^(-1).More importantly,when assembled with a K_(1.84)Ni[Fe(CN)_(6)]_(0.88)·0.49H_(2)O cathode,the full battery manifests excellent cycle stability and high rate performance.This study demonstrates the significant importance of the synergistic effect of structural regulation and electrolyte optimization in achieving high cycling stability of PIBs.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
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This publication is part of the grant PID2022-143003OB-I00 funded by MICIU/AEI/10.13039/501100011033 and by ERDF/EUDF acknowledges the grant PID2022-143003OB-I00 funded by MICIU/AEI/10.13039/501100011033 and by FSE+.
文摘The deployment of safe and high-energy density lithium metal polymer batteries(LMPBs)still requires further advances in the quest for new solid polymer electrolytes(SPEs).In this regard,salt anions have a decisive role in the overall SPE performance.While lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)was chosen earlier to have a highly flexible sulfonimide center and an extensively delocalized negative charge,it still suffers from several drawbacks ascribed to its poor interfacial compatibility with the lithium metal(LiM)anode and the fact that it is a PFAS.In this work,a novel lithium salt is cunningly designed,aiming to combine the advantages of previously reported lithium bis(fluorosulfonyl)imide(LiFSI)and lithium bis(difluoromethanesulfonyl)imide(LiDFSI)to overcome the limitations of the state-of-the-art SPE based on LiTFSI/poly(ethylene oxide)(PEO).The SPE containing the developed(difluoromethanesulfonyl)(fluorosulfonyl)imide(LiDFFSI)salt presented reduced interfacial resistance and improved compatibility with the lithium metal(LiM)anode compared with LiTFSI/PEO,enabled by the formation of a stable,uniform,and ionically conductive solid–electrolyte interphase(SEI).In addition,LiDFFSI-based SPEs demonstrated a prolonged cycling stability,achieving over 125 cycles at C/10 with minimal capacity fading in LiM||LiFePO_(4) cell configuration.These findings evidence how a rational design of the lithium salt chemistry allows tuning the formed SEI,directly impacting the overall SPE performance.Thus,LiDFFSI is presented as a promising alternative lithium salt to improve electrochemical performance and interfacial stability in next-generation LiM batteries.
基金This research was supported by the National Key R&D Program of China(2022YFB3506300)National Natural Science Foundation of China(No.52176185)+2 种基金Guangdong-Foshan Joint Fund(2023A1515140091)Guangdong High-level Innovation Institute project(2021B090905000)Ningbo Yongjiang Talent Introduction Program(2023A-184-G)Eastern Institute of Technology,Ningbo.
文摘Interfacial engineering,particularly the design of artificial solid-electrolyte interphases(SEIs),has been successfully applied in all-solid-state batteries(ASSLBs)for industrial applications.However,a fundamental understanding of the synthesis and mechanism models of artificial SEIs in all-solid-state Li-ion batteries remains limited.In this review,recent advances in designing and synthesizing artificial SEIs for ASSLBs to solve interfacial issues are thoroughly discussed,covering three main preparation methods and their technical routes:1)atomic layer deposition,2)sol-gel methods,and 3)mechanical ball-milling methods.Moreover,advanced ex-situ characterization techniques for artificial SEIs are comprehensively summarized.Finally,this review provides perspectives on techniques for the interface engineering of artificial SEIs for ASSLBs,with focus on promising methods for industrial applications.
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This work was financially supported by the National Natural Science Foundation of China(No.52102261)Natural Science Foundation of Jiangsu Province(No.BK20210942)+1 种基金Jiangsu Province Science and Technology Young Talents Promotion Project(No.KYZ21053)Changzhou Science and Technology Young Talents Promotion Project(Nos.KYZ21005 and KYZ21039).
文摘Aqueous rechargeable zinc ion batteries have received widespread attention due to their high energy density and low cost.However,zinc metal anodes face fatal dendrite growth and detrimental side reactions,which affect the cycle stability and practical application of zinc ion batteries.Here,an in-situ formed hierarchical solid-electrolyte interphase composed of InF3,In,and ZnF2 layers with outside-in orientation on the Zn anode(denoted as Zn@InF3)is developed by a sample InF3 coating.The inner ultrathin ZnF2 interface between Zn anode and InF3 layer formed by the spontaneous galvanic replacement reaction between InF3 and Zn,is conductive to achieving uniform Zn deposition and inhibits the growth of Zinc dendrites due to the high electrical resistivity and Zn2+conductivity.Meanwhile,the middle uniformly generated metallic In and outside InF3 layers functioning as corrosion inhibitor suppressing the side reaction due to the waterproof surfaces,good chemical inactivity,and high hydrogen evolution overpotential.Besides,the as-prepared zinc anode enables dendrite-free Zn plating/stripping for more than 6,000 h at nearly 100%coulombic efficiency(CE).Furthermore,coupled with the MnO2 cathode,the full battery exhibits the long cycle of up to 1,000 cycles with a low negative-to-positive electrode capacity(N/P)ratio of 2.8.
基金The National Natural Science Foundation of China(Nos.21203008,21975025,12274025 and 22372008)Hainan Province Science and Technology Special Fund(Nos.ZDYF2021SHFZ232 and ZDYF2023GXJS022)Hainan Province Postdoctoral Science Foundation(No.300333)supported this work.
文摘Sulfide-based solid-state electrolytes(SSEs)with high Li+conductivity(δLi^(+))and trifling grain boundaries have great potential for all-solid-state lithium-metal batteries(ASSLMBs).Nonetheless,the in-situ development of mixed ionic-electronic conducting solid-electrolyte interphase(SEI)at sulfide electrolyte/Li-metal anode interface induces uneven Li electrodeposition,which causes Li-dendrites and void formation,significantly severely deteriorating ASSLMBs.Herein,we propose a dual anionic,e.g.,F and N,doping strategy to Li7P3S11,tuning its composition in conjunction with the chemistry of SEI.Therefore,novel Li_(6.58)P_(2.76)N_(0.03)S_(10.12)F_(0.05)glass-ceramic electrolyte(Li_(7)P_(3)S_(11-5)LiF-3Li_(3)N-gce)achieved superior ionic(4.33 mS·cm^(−1))and lowest electronic conductivity of 4.33×10^(−10)S·cm^(−1)and thus,offered superior critical current density of 0.90 mA·cm^(−2)(2.5 times】Li7P3S11)at room temperature(RT).Notably,Li//Li cell with Li6.58P2.76N0.03S10.12F0.05-gce cycled stably over 1000 and 600 h at 0.2 and 0.3 mA·cm^(−2)credited to robust and highly conductive SEI(in-situ)enriched with LiF and Li3N species.Li3N’s wettability renders SEI to be highly Li+conductive,ensures an intimate interfacial contact,blocks reductive reactions,prevents Li-dendrites and facilitates fast Li+kinetics.Consequently,LiNi0.8Co0.15Al0.05O_(2)(NCA)/Li_(6.58)P_(2.76)N_(0.03)S_(10.12)F_(0.05)-gce/Li cell exhibited an outstanding first reversible capacity of 200.8/240.1 mAh·g^(−1)with 83.67%Coulombic efficiency,retained 85.11%of its original reversible capacity at 0.3 mA·cm^(−2)over 165 cycles at RT.
基金the financial support from the National Key Research and Development Program of China(2023YFB2504000)。
文摘High-voltage Li-rich Mn-based oxide(LRMO)cathodes are promising for breaking through the energy density limits of lithium-ion batteries,yet their practical application remains limited by electrochemical performance degradation caused by unstable cathode-electrolyte interphase(CEI)evolution during longterm cycling.To address this issue,we propose a novel surface modification strategy using La_(0.7)Sr_(0.3)MnO_(3-σ)(LSMO)nanodots,which exhibit high electronic co nductivity and excellent corrosion resistance.These nanodots act as stable anchoring sites,facilitating the formation of a robust CEI on LRMO,The LSMOmodified cathode demonstrates significantly improved anionic redox reversibility,effectively mitigating transition metal migration and lattice oxygen loss.Furthermore,the optimized interfacial electrochemical kinetics ensure sustained rapid Li+diffusion throughout cycling,while the formation of a stable trilayer CEI structure suppresses electrolyte decomposition.Benefiting from these synergistic effects,the LSMO nanodot-engineered LRMO cathode delivers outstanding cycling stability,retaining 97.4%capacity after 300 cycles at 1 C.This work not only highlights the critical role of nanodot heterostructures in stabilizing CEI but also provides a new approach to designing high-voltage cathodes with superior interfacial compatibility and long-term durability.
基金supported by the Key Laboratory of Sichuan Province for Lithium Resources Comprehensive Utilization and New Lithium Based Materials for Advanced Battery Technology(LRMKF202405)the National Natural Science Foundation of China(52402226)the Sichuan Provincial Natural Science Foundation (2024NSFSC1016)
文摘Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditions)faces significant challenges,including accelerated electrolyte decomposition,interfacial instability,and potential thermal runaway risks.To address these challenges,we present a solvation-interphase synergistic regulation strategy using 2-fluorobenzenesulfonamide(2-FBS)as a multifunctional electrolyte additive.The 2-FBS molecule effectively modulates the Li^(+)solvation structure by reducing the coordination of ethylene carbonate(EC)solvent.This transformation suppresses EC-induced parasitic reactions while scavenging superoxide radicals,thereby mitigating gas evolution at electrode interfaces.Upon preferential decomposition,2-FBS further promotes the formation of a robust LiF-Li_(3)N-Li_(2)S-rich interphase with exceptional mechanical strength(Young’s modulus:39.4 GPa).This inorganic-rich hybrid interphase simultaneously enables dendrite-free lithium plating and enhances cathode thermal stability.Consequently,2-FBS-modified electrolyte empowers LiCoO_(2)//Li cells to deliver 82.8%capacity retention after 800 cycles at 55°C and sustain 81.2%capacity retention after 1500 cycles at 4 C.Moreover,practical validation through nail penetration tests confirms the effectiveness of the electrolyte in preventing thermal propagation in fully charged pouch cells.This work establishes a paradigm for enabling reliable battery operation under extreme conditions through synergistic solvation and interphase engineering.
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support from the Heilongjiang Province"Double First Class"Discipline Collaborative Innovation Project(No.LJGXCG2023-061).
文摘Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions.In this study,we have tuned orbital hybridization states forming an interface enriched with sp^(2) hybridized carbon(sp^(2)-C),which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation.Benefiting from successfully constructed inorganic-rich SEI,the ICE increased to 91%and sodium storage capacity reached 346 mAh/g.Besides,the capacity retention rate was 90.7%after 700 cycles at 1 A/g higher than pristine electrode(83.8%).
基金supported by the National Key R&D Program of China(2021YFB3800300).
文摘High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.
基金supported by the National Natural Science Foundation of China(Nos.U21A20311 and 52400163).
文摘The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO_(2) battery by using trimethylsilyl isocyanate(TMIS)as electrolyte additive.The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI.By the synergistic action,the Co3+dissolution problem of the LiCoO_(2) cathode was effectively curbed.Furthermore,TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li^(+).As expected,the 4.6 V Li||LiCoO_(2) battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.
基金the financial support from the National Natural Science Foundation of China,China(Grant Nos.52502258 and 52162030)the Yunnan Fundamental Research Projects,China(Grant Nos.202501AT070298,202401AU070163 and 202401AT070368)+5 种基金the Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects,China(Grant No.2023-XMDJ-00617107)the Expert Workstation Support Project of Yunnan Province,China(Grant Nos.202405AF140069 and 202505AF350019)the University Service Key Industry Project of Yunnan Province,China(Grant No.FWCY-ZD2024005)the Shenzhen Science and Technology Program,China(Grant No.KJZD20230923114107014)the Scientific Research Foundation of Kunming University of Science and Technology,China(20220122)the Analysis and Test Foundation of Kunming University of Science and Technology,China(Grant No.2023T20220122)。
文摘Weakly solvating electrolytes(WSEs)promote the formation of anion-driven solid electrolyte interphases(SEI),enabling stable lithium metal batteries.However,current strategies involving alkylated modification,steric hindrance incorporation,coordinated oxygen(O)regulation,and selective fluorination face poor-diversity interfacial chemistry,high cost,or environmental concerns.Here,we propose a heteroatom-substitution strategy to design a WSE composed of lithium bis(fluorosulfonyl)imide(LiFSI)and 1,4-oxathiane(OTA)as a single solvent.Substituting oxygen with sulfur in conventional 1,4-dioxane(1,4-DX)generates OTA with a modulated dipole and charge distribution,weakening Li^(+)-OTA coordination while promoting anion-involved solvation sheath.This unique solvation structure triggers the formation of an inorganic-rich SEI with sulfur-containing species,enabling high Li plating/stripping coulombic efficiency and stable Li‖Li symmetric cells cycling for 1000 h.Benefiting from the superior interfacial chemistry and wettability of the electrolyte to the LiFePO_(4) cathode,full cells exhibit exceptional cycling stability even at low negative-to-positive(N/P)ratios,A pouch cell coupled with3.58 mAh cm^(-2) LiFePO_(4) and 20μm Li(N/P~1.15)maintains 88.77%capacity after 150 cycles.This work shows a fluorine-free solvent design paradigm for advanced WSEs,providing novel insights toward stable LMBs.
基金supported by the National Natural Science Foundation of China(No.22305106)the Postdoctoral Fellowship Program of CPSF(GZC20230682)Beijing Key Laboratory of High-Entropy Energy materials and Devices,Beijing Institute of Nanoenergy and Nanosystems(No.GS 2025ZD005)。
文摘Li_(7)La_(3)Zr_(2)O_(12)-based electrolytes have got great promise for solid-state lithium(Li)metal batteries because of their high elastic modulus and wide electrochemical stability window.However,the insufficient contact and heterogeneous Li deposition severely hinder their practical applications.Here,a flexible ternary polymethacrylate(PMA)matrix is designed to incorporate with Ta-doped Li_(7)La_(3)Zr_(2)O_(12)(LLZTO-PMA).The PMA matrix ensures excellent interfacial contact,while the synergistic effects of its polar carbonyl groups and its interaction with LLZTO creating fast interfacial Li^(+)pathways yield a high ionic conductivity of 0.266 mS cm^(-1)at 20℃.Moreover,the interaction between LLZTO and PMA matrix further guides the formation of a hybrid LiF/Li_(3)N-rich solid electrolyte interphase,which allows a fast Li^(+)interfacial kinetic due to its lowered Li^(+)diffusion barrier.Consequently,the LLZTO-PMA electrolyte contributes an ultra-stable Li anode interphase,attaining a lifespan exceeding 10,000 h in symmetric cells and retaining over 96%capacity after 600 cycles in full battery,demonstrating a breakthrough for high-performance solid-state batteries.
基金supports by Central South University Innovation-Driven Research Programme(2023CXQD038)the Fundamental Research Funds for the Central Universities of Central South University(2025ZZTS0089)supported by the High Performance Computing Center of Central South University.
文摘Anode-free sodium metal batteries(AFSMBs)have gained attention as next-generation storage systems with high energy density and cost-effectiveness.However,non-uniform sodium(Na)deposition and an unsteady solid electrolyte interphase(SEI)lead to dendrite-related issues and severe irreversible Na^(+)plating/stripping,greatly aggravating their cycle deterioration.In this study,we effectively modified the 3D current collector's electronic structure by introducing Zn-N_(x)active sites(Zn-CNF),which enhances lateral Na^(+)diffusion and the Na planar growth,enabling uniform deep Na deposition at an exceptionally high capacity of 10 mA h cm^(-2).Furthermore,the Zn-N_(x)bonds enhance the adsorption capacity of PF6and contribute to forming a stable inorganic-rich SEI layer.Consequently,Zn-CNF with the electronic structure regulation endows an ultra-low nucleation overpotential(8 mV)and ultra-high Coulombic efficiency of 99.94%over 1,600 cycles.Symmetric cells demonstrate stable Na^(+)plating/stripping behavior for more than 4,400 h at 1 mA cm^(-2).Moreover,under high cathode loading(7.97 mg cm^(-2)),the AFSMBs achieve a high energy density of 374 W h kg^(-1)and retain a high discharge capacity of 82.49 mA h g^(-1)with a capacity retention of 80.4%after 120 cycles.This work proposes a viable strategy to achieving high-energy-density AFSMBs.
基金supported by the National Natural Science Foundation of China(Grant No.52104333)the Program for Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(Grant No.NJYT24070)+1 种基金the Natural Science Foundation of Inner Mongolia(Grant No.2024MS05029)the Research Project of Carbon Peak and Carbon Neutrality in Universities of Inner Mongolia Autonomous Region(Grant No.STZX202316).
文摘The substantial influences of Mo contents varying from 0 to 0.26 and 0.50 wt.%on the microstructural evolution and MX(M=Nb,V and Mo;X=C and N)precipitation characteristics of Nb–V–N microalloyed steels processed by hot deformation and continuous cooling were studied using a Gleeble 3800 thermomechanical simulator.Metallographic analysis showed that the ferrite microstructure transformed from polygonal ferrite(PF)in 0Mo steel to both acicular ferrite(AF)and PF in 0.26Mo and 0.50Mo steels,and AF content first increased and then decreased.The thermodynamic calculations and the experimental results proved that the quantity of solid solution of Mo in austenite obviously increased,which reduced the austenite(γ)to ferrite(α)transformation temperature,consequently promoting AF formation in 0.26Mo steel and bainite transformation in 0.50Mo steel.Moreover,the submicron Nb-rich MX particles that precipitated at the temperature of the austenite region further induced AF heterogeneous nucleation with an orientation relationship of(100)_(MX)//(100)_(Ferrite)and[■][001]Ferrite.The interphase precipitation of the nanosized V-rich MX particles with Mo partitioning that precipitated duringγ→αtransformation exhibited a Baker–Nutting orientation relationship of(100)_(MX)//(100)Ferrite and[001]_(MX)//[■]_(Ferrite)with respect to the ferrite matrix.With increasing Mo content from 0 to 0.26 and 0.50 wt.%,the sheet spacing decreased from 46.9–49.0 to 34.6–38.6 and 25.7–28.0 nm,respectively,which evidently hindered dislocation movement and greatly enhanced precipitation strengthening.Furthermore,facilitating AF formation and interphase precipitation was beneficial to improving steel properties,and the optimal Mo content was 0.26 wt.%.
文摘Solid-state batteries have recently raised strong interest in the scientific community as possible advancement of battery technology beyond commercial lithium ion due to the promise of high energy densities and improved safety[1].In the core of development of high-performance solid-state batteries,is the development of solid-state electrolytes,which should be both sufficiently ionically conductive and offer stable interphases with high-energy electrodes,such as alkali metals and silicon[2,3].Recently,potassium-ion batteries have emerged as an alternative to lithium-ion batteries as a remedy to limited resources and uneven distribution of lithium,as well as due to the fact that low standard electrode potentials of K/K^(+) electrodes should lead to high operation voltages,competitive to those observed in commercial lithium batteries[4-6].
基金the financial support received from the National Natural Science Foundation of China(22378426,22138013)the Natural Science Foundation of Shandong Province(ZR2022MB088)the Taishan Scholar Project(ts201712020)。
文摘High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based electrolytes,particularly at extreme temperatures.In this study,we develop a stable electrolyte incorporating lithium difluorophosphate(LiDFP)as an additive to enhance the electrochemical performance of DIBs over a wide temperature range.LiDFP preferentially decomposes to form a rapid anion-transporting,mechanically robust CEI layer on graphite,which provides better protection by suppressing graphite's volume expansion,preventing electrolyte oxidative decomposition,and enhancing reaction kinetics.As a result,Li||graphite half cells using LiDFP electrolyte exhibit outstanding rate performance(90.8% capacity retention at 30 C)and excellent cycle stability(82.2% capacity retention after 5000 cycles)at room temperature.Moreover,graphite||graphite full cells with LiDFP electrolyte demonstrate stable discharge capacity across a temperature range of-20 to 40℃,expanding the potential applications of LiDFP.This work establishes a novel strategy for optimizing the interphase through electrolyte design,paving the way for all-climate DIBs with improved performance and stability.
基金supported by the National Natural Science Foundation of China(22179063,22479078,and 22409093)the Natural Science Foundation of Jiangsu Province of China(BK20240579)。
文摘FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium storage.Rational structural design is one way to overcome these drawbacks.In this work,MIL-88B-Fe-derived FeS_(2)nanoparticles/N-doped carbon nanofibers(M-FeS_(2)@CNFs)with expansion buffer capability are designed and synthesized for high-performance PIB anodes via electrospinning and subsequent sulfurization.The uniformly distributed cavity-type porous structure effectively mitigates the severe aggregation problem of FeS_(2)nanoparticles during cycling and buffers the volume change,further enhancing the potassium storage capacity.Meanwhile,the robust KF-rich solid electrolyte interphase induced by methyl trifluoroethylene carbonate(FEMC)additive improves the cycling stability of the M-FeS_(2)@CNF anode.In the electrolyte with 3 wt%FEMC,the M-FeS_(2)@CNF anode shows a reversible specific capacity of 592.7 mA h g^(-1)at 0.1 A g^(-1),an excellent rate capability of 327.1 mA h g^(-1)at 5 A g^(-1),and a retention rate 80.7%over 1000 cycles at 1 A g^(-1).More importantly,when assembled with a K_(1.84)Ni[Fe(CN)_(6)]_(0.88)·0.49H_(2)O cathode,the full battery manifests excellent cycle stability and high rate performance.This study demonstrates the significant importance of the synergistic effect of structural regulation and electrolyte optimization in achieving high cycling stability of PIBs.
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.
