Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified W...Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified WSE for fast-charging high-voltage LMBs,which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(TTE)into the tetrahydropyran(THP)based WSE.A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP,which accelerates the de-solvation kinetics of Li~+.Besides,more anions are involved in solvation structure in the presence of TTE,yielding inorganic-rich interphases with improved stability.Li(30μm)||Li Ni_(0.5)Co_(0.2)Mn_(0.3)O_(2)(4.1 mAh/cm^(2))batteries with the TTE modified WSE retain over 64%capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V,much better than that with pure THP based WSE.This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.展开更多
The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising propert...The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.展开更多
Development of advanced high-voltage electrolytes is key to achieving high-energy-density lithium metal batteries(LMBs).Weakly solvating electrolytes(WSE)can produce unique anion-driven interphasial chemistry via alte...Development of advanced high-voltage electrolytes is key to achieving high-energy-density lithium metal batteries(LMBs).Weakly solvating electrolytes(WSE)can produce unique anion-driven interphasial chemistry via altering the solvating power of the solvent,but it is difficult to dissolve the majority of Li salts and fail to cycle at a cut-off voltage above 4.5 V.Herein,we present a new-type WSE that is regulated by the anion rather than the solvent,and the first realize stable cycling of dimethoxyethane(DME)at 4.6 V without the use of the“solvent-in-salt”strategy.The relationships between the degree of dissociation of salts,the solvation structure of electrolytes,and the electrochemical performance of LMBs were systematically investigated.We found that LiBF_(4),which has the lowest degree of dissociation,can construct an anion-rich inner solvation shell,resulting in anion-derived anode/cathode interphases.Thanks to such unusual solvation structure and interphasial chemistry,the Li-LiCoO_(2)full cell with LiBF_(4)-based WSE could deliver excellent rate performance(115 mAh g^(-1)at 10 C)and outstanding cycling stability even under practical conditions,including high loading(10.7 mg cm^(-2)),thin Li(50μm),and limited electrolyte(1.2μL mg^(-1)).展开更多
Lithium(Li)batteries are major players in the power source market of electric vehicles and portable electronic devices.Electrolytes are critical to determining the performance of Li batteries.Conventional electrolytes...Lithium(Li)batteries are major players in the power source market of electric vehicles and portable electronic devices.Electrolytes are critical to determining the performance of Li batteries.Conventional electrolytes fall behind the ever-growing demands for fast-charging,wide-temperature operation,and safety properties of Li batteries.Despite the great success of(localized)high-concentration electrolytes,they still suffer from disadvantages,such as low ionic conductivity and high cost.Weakly solvating electrolytes(WSEs),also known as low-solvating electrolytes,offer another solution to these challenges,and they have attracted intensive research interests in recent years.This contribution reviews the working mechanisms,design principles,and recent advances in the development of WSEs.A summary and perspective regarding future research directions in this field is also provided.The insights will benefit academic and industrial communities in the design of safe and high-performance next-generation Li batteries.展开更多
Advanced electrolyte engineering is an important strategy for developing high-efficacy lithium(Li)metal batteries(LMBs).Unfortunately,the current electrolytes limit the scope for creating batteries that perform well o...Advanced electrolyte engineering is an important strategy for developing high-efficacy lithium(Li)metal batteries(LMBs).Unfortunately,the current electrolytes limit the scope for creating batteries that perform well over temperature ranges.Here,we present a new electrolyte design that uses fluorosulfonyl carboxylate as a non-solvating solvent to form difluoroxalate borate(DFOB-)anion-rich solvation sheath,to realize high-performance working of temperature-tolerant LMBs.With this optimized electrolyte,favorable SEI and CEI chemistries on Li metal anode and nickel-rich cathode are achieved,respectively,leading to fast Li^(+)transfer kinetics,dendrite-free Li deposition and suppressed electrolyte deterioration.Therefore,Li||LiNi_(0.80)Co_(0.15)Al_(0.05)O_(2)batteries with a thin Li foil(50μm)show a long-term cycling lifespan over 400 cycles at 1C and a superior capacity retention of 90%after 200 cycles at 0.5C under 25℃.Moreover,this electrolyte extends the operating temperature from-10 to 30℃and significantly improve the capacity retention and Coulombic efficiency of batteries are improved at high temperature(60℃).Fluorosulfonyl carboxylates thus have considerable potential for use in high-performance and allweather LMBs,which broadens the new exploring of electrolyte design.展开更多
Ether electrolytes for potassium-ion batteries exhibit a broader electrochemical window and greater applicability,yet most of them are high-concentration electrolytes with elevated cost.In this study,we propose the us...Ether electrolytes for potassium-ion batteries exhibit a broader electrochemical window and greater applicability,yet most of them are high-concentration electrolytes with elevated cost.In this study,we propose the use of a weakly solvating cyclic ether electrolyte with tetrahydropyran(THP)as the solvent.This approach induces the formation of a thin and dense inorganic-rich solid electrolyte interphase(SEI)film,which is accompanied by a decrease in the activation energy of electrode interfacial reactions due to the weak ligand binding of THP with K^(+).Density functional theory(DFT)simulations also corroborate the hypothesis that K^(+)has a lower binding energy with THP.During potassium storage process,the phenomenon of solvent co-intercalation of graphite does not occur,which greatly reduces the destruction of the graphite structure and enables a superior electrochemical performance and enhanced cycling stability at a lower concentration(2 M).At a current density of 0.2 C(55.8 mA·g^(-1)),the battery can be stably cycled for 800 cycles(approximately 8 months)with a specific capacity of 171.8 mAh·g^(-1).This study provides a new ether-based electrolyte for potassium ion batteries and effectively reduces the electrolyte cost,which is expected to inspire further development of energy storage batteries.展开更多
Lithium-sulfur(Li-S)batteries hold great promise to be the next-generation candidate for high-energy-density secondary batteries but in the prerequisite of using low electrolyte-to-sulfur(E/S)ratios.Highly solvating e...Lithium-sulfur(Li-S)batteries hold great promise to be the next-generation candidate for high-energy-density secondary batteries but in the prerequisite of using low electrolyte-to-sulfur(E/S)ratios.Highly solvating electrolytes(HSEs)and sparingly solvating electrolytes(SSEs),with opposite nature towards the dissolution of polysulfides,have recently emerged as two effective solutions to decrease the E/S ratio and increase the overall practical energy density of Li-S batteries.HSEs featuring with high polysulfide solvation ability have the potential to reduce the E/S ratio by dissolving more polysulfides with less electrolyte,while SSEs alter the sulfur reaction pathway from a dissolution-precipitation mechanism to a quasi-solid mechanism,thereby independent on the use of electrolyte amount.Both HSEs and SSEs show respective effectiveness in lean-electrolyte Li-S batteries,but encounter different challenges to bring Li-S batteries into practical application.This review aims to present a comparative discussion on their unique features and basic electrochemical reaction mechanisms in practical lean-electrolyte Li-S batteries.Emphasis is focused on the current technical challenges and possible solutions for their future development.展开更多
Li^(+) solvation structures have a decisive influence on the electrode/electrolyte interfacial properties and battery performances.Reduced salt concentration may result in an organic rich solid electrolyte interface(S...Li^(+) solvation structures have a decisive influence on the electrode/electrolyte interfacial properties and battery performances.Reduced salt concentration may result in an organic rich solid electrolyte interface(SEI)and catastrophic cycle stability,which makes low concentration electrolytes(LCEs)rather challenging.Solvents with low solvating power bring in new chances to LCEs due to the weak salt-solvent interactions.Herein,an LCE with only 0.25 mol L^(-1) salt is prepared with fluoroethylene carbonate(FEC)and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)).Molecular dynamics simulations and experiments prove that the low solvating power solvent FEC not only renders reduced desolvation energy to Li^(+) and improves the battery kinetics,but also promotes the formation of a LiF-rich SEI that hinders the electrolyte consumption.Li||Cu cell using the LCE shows a high coulombic efficiency of 99.20%,and LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)||Li cell also exhibits satisfying capacity retention of 89.93%in 200 cycles,which demonstrates the great potential of solvating power regulation in LCEs development.展开更多
Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.H...Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.Herein,the ester solvent of methyl propionate(MP)with low melting point and low viscosity was used to tackle ion transport difficulty in electrolytes.Fluorinated ester was further added to accelerate interfacial transport through intermolecular interactions.The influence of fluorinated esters with different fluorination degrees on the solvation structure of electrolytes and the performance of batteries was further studied.As a result,methyl pentafluoropropionate(M5F)with five fluorine atoms was selected for its optimal interactions with both Li+and MP solvent in the primary solvation structure,contributing to desired solvation structure for fast interfacial transport.The LiFePO4(LFP)||graphite cell with LiFSI-MP-M5F electrolyte exhibited a high cyclability of 85.8%after 120 cycles and retained 81.2%of room-temperature capacity when charged and discharged at−30℃.1 Ah LFP||graphite pouch cell with high cathode loading(20 mg/cm^(2))in LiFSI-MP-M5F electrolyte exhibited 0.85 Ah capacity when charged and discharged at−20℃.This work provides a guidance for electrolyte design by synergistic fluorinated and non-fluorinated solvents for LIBs at low-temperature application.展开更多
Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle ...Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle this challenge by introducing n-hexane as an electrolyte additive to weaken LiClO4 ionization,achieving minimized dissociation via squeezed solvation shells with compact ion pairs.Molecular dynamics simulations and experimental characterizations reveal that n-hexane enriches anion coordination around Li+,endowing the electrolyte with robust anti-reduction capability.This suppresses SEI overgrowth,reduces interfacial resistance,and accelerates N2 diffusion.Consequently,a thinner,inorganic-rich SEI is formed,enabling high nitrogen flux and rapid active Li3N generation kinetics.Consequently,the proof-of-concept system achieves unprecedentedly high Faradaic efficiency of 53.8%±8.2%at 10 mA cm^(−2)and NH_(3) yield rate of 88.57±9.5 nmol s^(−1)cm^(−2)under ambient conditions,making a giant step further toward industrializing the electrochemical ammonia production.展开更多
Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temp...Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.展开更多
The sluggish kinetics of oxygen evolution reaction(OER)is a significant bottleneck for green hydrogen production via water electrolysis[1].Despite intensive efforts to develop advanced OER electrocatalysts featuring l...The sluggish kinetics of oxygen evolution reaction(OER)is a significant bottleneck for green hydrogen production via water electrolysis[1].Despite intensive efforts to develop advanced OER electrocatalysts featuring low noble-metal content and high activity,high overpotential and rapid degradation at high potentials persist.This inherent trade-off between activity and stability underscores the importance of designing catalysts that can deliver high OER activity at lower operating potentials,thereby efficiently mitigating dissolution and extending 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
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
The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from ...The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from the hydrogen evolution reaction(HER).A new paradigm capable of transcending current selectivity constraints is urgently required to advance eNRR toward industrial implementation.In this work,we propose two practical selectivity descriptors(ΔΔG andΔU)based on a systematic investigation of the potential-dependent competition between eNRR and HER on confined dual-atom catalysts.The descriptorΔΔG(G_(N_(2))-ΔG_(H))identifies the potential range where N_(2)adsorption dominates over H adsorption,whileΔU(U_(cross)-U_(eNRR))specifies the potential range to trigger direct eNRR,offering a quantitative benchmark for rational catalyst design.Ideal catalysts should maintain N_(2)-preferential adsorption across a broad potential window to facilitate direct eNRR.Guided by this insight,we demonstrate that confined dual-atom configurations with optimized interatomic distances can simultaneously achieve both overwhelming N_(2)adsorption and sufficient activation,thereby overcoming the conventional selectivity limitations.This strategy enables ammonia synthesis with industrially relevant production rates and current density even at elevated potentials.Our mechanistic insights not only elucidate the root causes of performance limitations in eNRR but also offer a rational design framework for developing high-performance catalysts across a broad range of electrochemical transformations.展开更多
Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(...Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(TA)is proposed as an effective electrolyte additive that modulates the Zn^(2+)deposition environment via coordination competition.The polar functional groups of TA restructure the solvation sheath,while its molecular dipoles generate localized electric fields that accelerate Zn^(2+)migration and promote directional(002)-oriented deposition.These effects collectively suppress side reactions and enhance Zn plating/stripping reversibility.The four hydroxyl(–OH)and conjugated ketone groups(C=O)in the TA molecule have strong coordination ability(Lewis basicity)and can form a stable[Zn(TA)(H_(2)O)_(n)]^(2+)with Zn^(2+),reducing the number of free water molecules and the proportion of active water in the solvation sheath.The TA molecules are adsorbed onto the Zn anode surface,leading to the redistribution of the local spatial electric field and homogenization of ion flux dynamics.Its conjugated planar structure can induce Zn^(2+)to preferentially deposit along the(002)crystal plane.Zn//Zn symmetric cell using TA-containing ZnSO4 electrolyte exhibits stable cycling for more than 2240 h at 1 mA cm^(−2),1 mAh cm^(−2).The Zn//activated carbon(AC)full-cell can stably cycle 30,000 cycles at 5 A g^(−1)with a capacity retention rate of 90%.This study provides important insights into electrolyte engineering strategies for stabilizing Zn anodes,highlighting the potential of molecular design additives in next-generation Zn^(2+)energy storage systems.展开更多
Aqueous zinc-ion batteries(AZIBs)offer a safe,cost-effective,and high-capacity energy storage solution,yet their performance is hindered by interfacial challenges at the Zn anode,including hydrogen evolution,corrosion...Aqueous zinc-ion batteries(AZIBs)offer a safe,cost-effective,and high-capacity energy storage solution,yet their performance is hindered by interfacial challenges at the Zn anode,including hydrogen evolution,corrosion,and dendritic Zn growth.While most studies focus on regulating Zn~(2+)solvation structures in bulk electrolytes,the evolution of interfacial solvation—where Zn~(2+)undergoes desolvation and deposition—remains insufficiently explored.Here,we introduce sulfated nanocellulose(SNC),an anion-rich biopolymer,to tailor the interfacial solvation structure without altering the bulk electrolyte composition.Using in situ attenuated total reflection Fourier transform infrared spectroscopy and fluorescence interface-extended X-ray absorption fine structure,we reveal that SNC facilitates the formation of a low-coordinated Zn~(2+)solvation shell at the interface by weakening H_(2)O coordination.This transformation is driven by electrostatic interactions between Zn~(2+)and anchored sulfate groups,thereby reducing water activity,improving interfacial stability during charge/discharge,and suppressing parasitic reactions.Consequently,a high average coulombic efficiency of 99.6%over 500 cycles in Zn|Ti asymmetric cells and 1.5 Ah pouch cells(13.4 mg cm^(-2)loading,remained stable over 250 cycles)were achieved in SNC-induced AZIBs.This work underscores the importance of interfacial solvation structure engineering—beyond traditional bulk electrolyte design—in enabling practical,high-performance AZIBs.展开更多
The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by ca...The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores,interparticle voids between MOF particles readily absorb liquid electrolyte,obscuring our understanding of the intrinsic role of nanopores in directing Li^(+)transport.To address this challenge,we introduce a one-dimensional(1D)MOF model architecture that eliminates interparticle effects and enables direct observation of Li^(+)solvation and de-solvation dynamics.Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors,supported by both experimental measurements and neural network potential-based molecular dynamics simulations.Building on these insights,we construct a hierarchical core-shell MOF architecture by integrating ZIF-8(core)and HKUST-1(shell)onto a hybrid fiber scaffold.This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways,directional Li^(+)conduction,and improved thermal and electrochemical resilience.展开更多
The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit e...The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit exceptional electrochemical stability and compatibility with electrode electrolyte interfaces(EEIs),two major challenges persist:(i)safety risks caused by excessive low-flash-point diluents,and(ii)insufficient understanding of how diluents modulate solvation structures.Herein,we introduce a low-diluent-content LCILE system composed of lithium bis(fluorosulfonyl)imide(LiFSI)salt,N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide(Pyr_(13)FSI)ionic liquid,and trifluoromethanesulfonate(TFS)diluent.The TFS diluent strengthens ion-ion interactions by lowering the dielectric constant of the electrolyte,resulting in the formation of a unique nanometric anion aggregates(N-AGGs)reinforced solvation structure.These large anionic clusters exhibit accelerated redox decomposition kinetics,facilitating the rapid formation of a thin,dense,and low-impedance EEI.Consequently,the Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)coin cell achieves 87.8%capacity retention over 300 cycles at 4.3 V,while a practical 1.4 Ah Li/NCM622 pouch cell retains 84.5%capacity after 80 cycles at 4.5 V.Furthermore,the electrolyte demonstrates exceptional safety,and 2 Ah Li metal pouch cells successfully pass rigorous nail penetration tests without any ignition or explosion.This work not only provides a design strategy for intrinsically safe and high-performance electrolytes but also highlights the critical role of anion cluster decomposition kinetics in shaping EEI formation.展开更多
基金supported by Hengyang City,Hunan Province Science and Technology Innovation Project(No.202250045319)the National Natural Science Foundation of China(Nos.11375084,21808125)the Scientific Research Planning Project of Jilin Provincial Education Department(No.JJKH20241249KJ)。
文摘Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified WSE for fast-charging high-voltage LMBs,which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(TTE)into the tetrahydropyran(THP)based WSE.A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP,which accelerates the de-solvation kinetics of Li~+.Besides,more anions are involved in solvation structure in the presence of TTE,yielding inorganic-rich interphases with improved stability.Li(30μm)||Li Ni_(0.5)Co_(0.2)Mn_(0.3)O_(2)(4.1 mAh/cm^(2))batteries with the TTE modified WSE retain over 64%capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V,much better than that with pure THP based WSE.This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.
基金financially supported by National Natural Science Foundation of China(52003231,22065037)Yunnan Fundamental Research Projects(202201AW070015)。
文摘The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.
基金supported by the Key Program for International S&T Cooperation Projects of China(No.2017YFE0124300)National Natural Science Foundation of China(Nos.51971002,52171205 and 52171197)+1 种基金Natural Science Foundation of Anhui Provincial Education Department(KJ2021A0393)Anhui Provincial Natural Science Foundation for Excellent Youth Scholars(No.2108085Y16).
文摘Development of advanced high-voltage electrolytes is key to achieving high-energy-density lithium metal batteries(LMBs).Weakly solvating electrolytes(WSE)can produce unique anion-driven interphasial chemistry via altering the solvating power of the solvent,but it is difficult to dissolve the majority of Li salts and fail to cycle at a cut-off voltage above 4.5 V.Herein,we present a new-type WSE that is regulated by the anion rather than the solvent,and the first realize stable cycling of dimethoxyethane(DME)at 4.6 V without the use of the“solvent-in-salt”strategy.The relationships between the degree of dissociation of salts,the solvation structure of electrolytes,and the electrochemical performance of LMBs were systematically investigated.We found that LiBF_(4),which has the lowest degree of dissociation,can construct an anion-rich inner solvation shell,resulting in anion-derived anode/cathode interphases.Thanks to such unusual solvation structure and interphasial chemistry,the Li-LiCoO_(2)full cell with LiBF_(4)-based WSE could deliver excellent rate performance(115 mAh g^(-1)at 10 C)and outstanding cycling stability even under practical conditions,including high loading(10.7 mg cm^(-2)),thin Li(50μm),and limited electrolyte(1.2μL mg^(-1)).
基金supported by the Hong Kong Polytechnic University(No.CDBJ)Z.Wang thanks the funding support from the Centrally Funded Postdoctoral Fellowship Scheme of the Hong Kong Polytechnic University(No.1-YXAU).
文摘Lithium(Li)batteries are major players in the power source market of electric vehicles and portable electronic devices.Electrolytes are critical to determining the performance of Li batteries.Conventional electrolytes fall behind the ever-growing demands for fast-charging,wide-temperature operation,and safety properties of Li batteries.Despite the great success of(localized)high-concentration electrolytes,they still suffer from disadvantages,such as low ionic conductivity and high cost.Weakly solvating electrolytes(WSEs),also known as low-solvating electrolytes,offer another solution to these challenges,and they have attracted intensive research interests in recent years.This contribution reviews the working mechanisms,design principles,and recent advances in the development of WSEs.A summary and perspective regarding future research directions in this field is also provided.The insights will benefit academic and industrial communities in the design of safe and high-performance next-generation Li batteries.
基金the support from the Key-Area Research and Development Program of Guangdong Province (2020B090919003)the Yunnan Major Scientific and Technological Projects (202202AG050003)+4 种基金the Natural Science Foundation of China (22202078, 51904135,52162030)the Department of Education of Guangdong Province(2020KQNCX082)the Applied Basic Research Foundation of Yunnan Province (202103AA080019)the National Key R&D Program of China (2018YFB01040)the support of the supported by the Testing Technology Center of Materials and Devices of Tsinghua Shenzhen International Graduate School (SIGS)
文摘Advanced electrolyte engineering is an important strategy for developing high-efficacy lithium(Li)metal batteries(LMBs).Unfortunately,the current electrolytes limit the scope for creating batteries that perform well over temperature ranges.Here,we present a new electrolyte design that uses fluorosulfonyl carboxylate as a non-solvating solvent to form difluoroxalate borate(DFOB-)anion-rich solvation sheath,to realize high-performance working of temperature-tolerant LMBs.With this optimized electrolyte,favorable SEI and CEI chemistries on Li metal anode and nickel-rich cathode are achieved,respectively,leading to fast Li^(+)transfer kinetics,dendrite-free Li deposition and suppressed electrolyte deterioration.Therefore,Li||LiNi_(0.80)Co_(0.15)Al_(0.05)O_(2)batteries with a thin Li foil(50μm)show a long-term cycling lifespan over 400 cycles at 1C and a superior capacity retention of 90%after 200 cycles at 0.5C under 25℃.Moreover,this electrolyte extends the operating temperature from-10 to 30℃and significantly improve the capacity retention and Coulombic efficiency of batteries are improved at high temperature(60℃).Fluorosulfonyl carboxylates thus have considerable potential for use in high-performance and allweather LMBs,which broadens the new exploring of electrolyte design.
基金financial support from the National Key Research and Development Program of China(No.2022YFB2404300)the National Natural Science Foundation of China(Nos.22409153 and 52101269).
文摘Ether electrolytes for potassium-ion batteries exhibit a broader electrochemical window and greater applicability,yet most of them are high-concentration electrolytes with elevated cost.In this study,we propose the use of a weakly solvating cyclic ether electrolyte with tetrahydropyran(THP)as the solvent.This approach induces the formation of a thin and dense inorganic-rich solid electrolyte interphase(SEI)film,which is accompanied by a decrease in the activation energy of electrode interfacial reactions due to the weak ligand binding of THP with K^(+).Density functional theory(DFT)simulations also corroborate the hypothesis that K^(+)has a lower binding energy with THP.During potassium storage process,the phenomenon of solvent co-intercalation of graphite does not occur,which greatly reduces the destruction of the graphite structure and enables a superior electrochemical performance and enhanced cycling stability at a lower concentration(2 M).At a current density of 0.2 C(55.8 mA·g^(-1)),the battery can be stably cycled for 800 cycles(approximately 8 months)with a specific capacity of 171.8 mAh·g^(-1).This study provides a new ether-based electrolyte for potassium ion batteries and effectively reduces the electrolyte cost,which is expected to inspire further development of energy storage batteries.
基金The authors acknowledge the support from the National Natural Science Foundation of China(Nos.U2002213 and 51972219)the Science and Technology Development Fund Macao SAR(No.0077/2021/A2),the Collaborative Innovation Center of Suzhou Nano Science and Technology,the 111 Project,and the Joint International Research Laboratory of Carbon-based Functional Materials and Devices.
文摘Lithium-sulfur(Li-S)batteries hold great promise to be the next-generation candidate for high-energy-density secondary batteries but in the prerequisite of using low electrolyte-to-sulfur(E/S)ratios.Highly solvating electrolytes(HSEs)and sparingly solvating electrolytes(SSEs),with opposite nature towards the dissolution of polysulfides,have recently emerged as two effective solutions to decrease the E/S ratio and increase the overall practical energy density of Li-S batteries.HSEs featuring with high polysulfide solvation ability have the potential to reduce the E/S ratio by dissolving more polysulfides with less electrolyte,while SSEs alter the sulfur reaction pathway from a dissolution-precipitation mechanism to a quasi-solid mechanism,thereby independent on the use of electrolyte amount.Both HSEs and SSEs show respective effectiveness in lean-electrolyte Li-S batteries,but encounter different challenges to bring Li-S batteries into practical application.This review aims to present a comparative discussion on their unique features and basic electrochemical reaction mechanisms in practical lean-electrolyte Li-S batteries.Emphasis is focused on the current technical challenges and possible solutions for their future development.
基金supported by the National Key Research and Development Program of China(2019YFA0705603)the National Natural Science Foundation of China(22078341)+1 种基金the Natural Science Foundation of Hebei Province(B2020103028)financial support from York University。
文摘Li^(+) solvation structures have a decisive influence on the electrode/electrolyte interfacial properties and battery performances.Reduced salt concentration may result in an organic rich solid electrolyte interface(SEI)and catastrophic cycle stability,which makes low concentration electrolytes(LCEs)rather challenging.Solvents with low solvating power bring in new chances to LCEs due to the weak salt-solvent interactions.Herein,an LCE with only 0.25 mol L^(-1) salt is prepared with fluoroethylene carbonate(FEC)and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)).Molecular dynamics simulations and experiments prove that the low solvating power solvent FEC not only renders reduced desolvation energy to Li^(+) and improves the battery kinetics,but also promotes the formation of a LiF-rich SEI that hinders the electrolyte consumption.Li||Cu cell using the LCE shows a high coulombic efficiency of 99.20%,and LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)||Li cell also exhibits satisfying capacity retention of 89.93%in 200 cycles,which demonstrates the great potential of solvating power regulation in LCEs development.
基金supported by the National Key R&D Program of China(No.2022YFB3803400)National Natural Science Foundation of China(Nos.52102054,52020105010,51927803,52188101 and 52072378)+1 种基金Liaoning Province Science and Technology Planning Project(No.2022-BS-007)Fujian Science and Technology Program(No.2023T3025).
文摘Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.Herein,the ester solvent of methyl propionate(MP)with low melting point and low viscosity was used to tackle ion transport difficulty in electrolytes.Fluorinated ester was further added to accelerate interfacial transport through intermolecular interactions.The influence of fluorinated esters with different fluorination degrees on the solvation structure of electrolytes and the performance of batteries was further studied.As a result,methyl pentafluoropropionate(M5F)with five fluorine atoms was selected for its optimal interactions with both Li+and MP solvent in the primary solvation structure,contributing to desired solvation structure for fast interfacial transport.The LiFePO4(LFP)||graphite cell with LiFSI-MP-M5F electrolyte exhibited a high cyclability of 85.8%after 120 cycles and retained 81.2%of room-temperature capacity when charged and discharged at−30℃.1 Ah LFP||graphite pouch cell with high cathode loading(20 mg/cm^(2))in LiFSI-MP-M5F electrolyte exhibited 0.85 Ah capacity when charged and discharged at−20℃.This work provides a guidance for electrolyte design by synergistic fluorinated and non-fluorinated solvents for LIBs at low-temperature application.
基金supported by the National Natural Science Foundation of China (Grant No. U21A20332)support from the Collaborative Innovation Center of Suzhou Nano Science and Technology
文摘Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle this challenge by introducing n-hexane as an electrolyte additive to weaken LiClO4 ionization,achieving minimized dissociation via squeezed solvation shells with compact ion pairs.Molecular dynamics simulations and experimental characterizations reveal that n-hexane enriches anion coordination around Li+,endowing the electrolyte with robust anti-reduction capability.This suppresses SEI overgrowth,reduces interfacial resistance,and accelerates N2 diffusion.Consequently,a thinner,inorganic-rich SEI is formed,enabling high nitrogen flux and rapid active Li3N generation kinetics.Consequently,the proof-of-concept system achieves unprecedentedly high Faradaic efficiency of 53.8%±8.2%at 10 mA cm^(−2)and NH_(3) yield rate of 88.57±9.5 nmol s^(−1)cm^(−2)under ambient conditions,making a giant step further toward industrializing the electrochemical ammonia production.
基金the financial support from the Key Project of Shaanxi Provincial Natural Science Foundation-Key Project of Laboratory(2025SYS-SYSZD-117)the Natural Science Basic Research Program of Shaanxi(2025JCYBQN-125)+8 种基金Young Talent Fund of Xi'an Association for Science and Technology(0959202513002)the Key Industrial Chain Technology Research Program of Xi'an(24ZDCYJSGG0048)the Key Research and Development Program of Xianyang(L2023-ZDYF-SF-077)Postdoctoral Fellowship Program of CPSF(GZC20241442)Shaanxi Postdoctoral Science Foundation(2024BSHSDZZ070)Research Funds for the Interdisciplinary Projects,CHU(300104240913)the Fundamental Research Funds for the Central Universities,CHU(300102385739,300102384201,300102384103)the Scientific Innovation Practice Project of Postgraduate of Chang'an University(300103725063)the financial support from the Australian Research Council。
文摘Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.
文摘The sluggish kinetics of oxygen evolution reaction(OER)is a significant bottleneck for green hydrogen production via water electrolysis[1].Despite intensive efforts to develop advanced OER electrocatalysts featuring low noble-metal content and high activity,high overpotential and rapid degradation at high potentials persist.This inherent trade-off between activity and stability underscores the importance of designing catalysts that can deliver high OER activity at lower operating potentials,thereby efficiently mitigating dissolution and extending 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(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supported by the Taishan Scholar Program of Shandong Province(tsqn202507090)Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(CPSF)(GZB20250022)+1 种基金Natural Science Foundation of Shandong Province(ZR2025QC1086)Young Talents Project at Ocean University of China。
文摘The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from the hydrogen evolution reaction(HER).A new paradigm capable of transcending current selectivity constraints is urgently required to advance eNRR toward industrial implementation.In this work,we propose two practical selectivity descriptors(ΔΔG andΔU)based on a systematic investigation of the potential-dependent competition between eNRR and HER on confined dual-atom catalysts.The descriptorΔΔG(G_(N_(2))-ΔG_(H))identifies the potential range where N_(2)adsorption dominates over H adsorption,whileΔU(U_(cross)-U_(eNRR))specifies the potential range to trigger direct eNRR,offering a quantitative benchmark for rational catalyst design.Ideal catalysts should maintain N_(2)-preferential adsorption across a broad potential window to facilitate direct eNRR.Guided by this insight,we demonstrate that confined dual-atom configurations with optimized interatomic distances can simultaneously achieve both overwhelming N_(2)adsorption and sufficient activation,thereby overcoming the conventional selectivity limitations.This strategy enables ammonia synthesis with industrially relevant production rates and current density even at elevated potentials.Our mechanistic insights not only elucidate the root causes of performance limitations in eNRR but also offer a rational design framework for developing high-performance catalysts across a broad range of electrochemical transformations.
基金supported by the National Natural Science Foundation of China(22269020,42167068,U23A20582)the Gansu Province Higher Education Industry Support Plan Project(2023CYZC-17,2023CYZC-68)+1 种基金the Key Project of Natural Science Foundation of Gansu Province(25JRRA004)2024 Major Cultivation Project for University Research and Innovation Platforms(2024CXPT-10).
文摘Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(TA)is proposed as an effective electrolyte additive that modulates the Zn^(2+)deposition environment via coordination competition.The polar functional groups of TA restructure the solvation sheath,while its molecular dipoles generate localized electric fields that accelerate Zn^(2+)migration and promote directional(002)-oriented deposition.These effects collectively suppress side reactions and enhance Zn plating/stripping reversibility.The four hydroxyl(–OH)and conjugated ketone groups(C=O)in the TA molecule have strong coordination ability(Lewis basicity)and can form a stable[Zn(TA)(H_(2)O)_(n)]^(2+)with Zn^(2+),reducing the number of free water molecules and the proportion of active water in the solvation sheath.The TA molecules are adsorbed onto the Zn anode surface,leading to the redistribution of the local spatial electric field and homogenization of ion flux dynamics.Its conjugated planar structure can induce Zn^(2+)to preferentially deposit along the(002)crystal plane.Zn//Zn symmetric cell using TA-containing ZnSO4 electrolyte exhibits stable cycling for more than 2240 h at 1 mA cm^(−2),1 mAh cm^(−2).The Zn//activated carbon(AC)full-cell can stably cycle 30,000 cycles at 5 A g^(−1)with a capacity retention rate of 90%.This study provides important insights into electrolyte engineering strategies for stabilizing Zn anodes,highlighting the potential of molecular design additives in next-generation Zn^(2+)energy storage systems.
基金the National Natural Science Foundation of China(No.22379047)Yinzhou R&D Team(X.W.)+2 种基金Guangdong Basic and Applied Basic Research Foundation(2022B1515120019)the Project Funded by the China Scholarship Council(No.202108320278)the support from the Vacuum Interconnected Nanotech Workstation(Nano-X)from Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences(SINANO)。
文摘Aqueous zinc-ion batteries(AZIBs)offer a safe,cost-effective,and high-capacity energy storage solution,yet their performance is hindered by interfacial challenges at the Zn anode,including hydrogen evolution,corrosion,and dendritic Zn growth.While most studies focus on regulating Zn~(2+)solvation structures in bulk electrolytes,the evolution of interfacial solvation—where Zn~(2+)undergoes desolvation and deposition—remains insufficiently explored.Here,we introduce sulfated nanocellulose(SNC),an anion-rich biopolymer,to tailor the interfacial solvation structure without altering the bulk electrolyte composition.Using in situ attenuated total reflection Fourier transform infrared spectroscopy and fluorescence interface-extended X-ray absorption fine structure,we reveal that SNC facilitates the formation of a low-coordinated Zn~(2+)solvation shell at the interface by weakening H_(2)O coordination.This transformation is driven by electrostatic interactions between Zn~(2+)and anchored sulfate groups,thereby reducing water activity,improving interfacial stability during charge/discharge,and suppressing parasitic reactions.Consequently,a high average coulombic efficiency of 99.6%over 500 cycles in Zn|Ti asymmetric cells and 1.5 Ah pouch cells(13.4 mg cm^(-2)loading,remained stable over 250 cycles)were achieved in SNC-induced AZIBs.This work underscores the importance of interfacial solvation structure engineering—beyond traditional bulk electrolyte design—in enabling practical,high-performance AZIBs.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2023-00217581)supported by the Nano&Material Technology Development Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(RS-2024-00406724)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(RS-2025-25430676)。
文摘The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores,interparticle voids between MOF particles readily absorb liquid electrolyte,obscuring our understanding of the intrinsic role of nanopores in directing Li^(+)transport.To address this challenge,we introduce a one-dimensional(1D)MOF model architecture that eliminates interparticle effects and enables direct observation of Li^(+)solvation and de-solvation dynamics.Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors,supported by both experimental measurements and neural network potential-based molecular dynamics simulations.Building on these insights,we construct a hierarchical core-shell MOF architecture by integrating ZIF-8(core)and HKUST-1(shell)onto a hybrid fiber scaffold.This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways,directional Li^(+)conduction,and improved thermal and electrochemical resilience.
基金supported by the National Key R&D Program of China(Grant No.2022YFE0207300)the National Natural Science Foundation of China(Grant Nos.22179142 and 22075314)+1 种基金Jiangsu Provincial Science and Technology Program(Grant No.BG 2024020).XPSWAXS and TOF-SIMS characterizations were supported by Nano-X(Vacuum Interconnected Nanotech Workstation,Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences(SINANO),Suzhou 215123,China)。
文摘The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit exceptional electrochemical stability and compatibility with electrode electrolyte interfaces(EEIs),two major challenges persist:(i)safety risks caused by excessive low-flash-point diluents,and(ii)insufficient understanding of how diluents modulate solvation structures.Herein,we introduce a low-diluent-content LCILE system composed of lithium bis(fluorosulfonyl)imide(LiFSI)salt,N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide(Pyr_(13)FSI)ionic liquid,and trifluoromethanesulfonate(TFS)diluent.The TFS diluent strengthens ion-ion interactions by lowering the dielectric constant of the electrolyte,resulting in the formation of a unique nanometric anion aggregates(N-AGGs)reinforced solvation structure.These large anionic clusters exhibit accelerated redox decomposition kinetics,facilitating the rapid formation of a thin,dense,and low-impedance EEI.Consequently,the Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)coin cell achieves 87.8%capacity retention over 300 cycles at 4.3 V,while a practical 1.4 Ah Li/NCM622 pouch cell retains 84.5%capacity after 80 cycles at 4.5 V.Furthermore,the electrolyte demonstrates exceptional safety,and 2 Ah Li metal pouch cells successfully pass rigorous nail penetration tests without any ignition or explosion.This work not only provides a design strategy for intrinsically safe and high-performance electrolytes but also highlights the critical role of anion cluster decomposition kinetics in shaping EEI formation.
