Practical Zn metal batteries have been hindered by several challenges,including Zn dendrite growth,undesirable side reactions,and unstable electrode/electrolyte interface.These issues are particularly more serious in ...Practical Zn metal batteries have been hindered by several challenges,including Zn dendrite growth,undesirable side reactions,and unstable electrode/electrolyte interface.These issues are particularly more serious in low-concentration electrolytes.Herein,we design a Zn salt-mediated electrolyte with in situ ring-opening polymerization of the small molecule organic solvent.The Zn(TFSI)_(2)salt catalyzes the ring-opening polymerization of(1,3-dioxolane(DOL)),generating oxidation-resistant and non-combustible long-chain polymer(poly(1,3-dioxolane)(pDOL)).The pDOL reduces the active H_(2)O molecules in electrolyte and assists in forming stable organic–inorganic gradient solid electrolyte interphase with rich organic constituents,ZnO and ZnF_(2).The introduction of pDOL endows the electrolyte with several advantages:excellent Zn dendrite inhibition,improved corrosion resistance,widened electrochemical window(2.6 V),and enhanced low-temperature performance(freezing point=-34.9°C).Zn plating/stripping in pDOL-enhanced electrolyte lasts for 4200 cycles at 99.02%Coulomb efficiency and maintains a lifetime of 8200 h.Moreover,Zn metal anodes deliver stable cycling for 2500 h with a high Zn utilization of 60%.A Zn//VO_(2)pouch cell assembled with lean electrolyte(electrolyte/capacity(E/C=41 mL(Ah)^(-1))also demonstrates a capacity retention ratio of 92%after 600 cycles.These results highlight the promising application prospects of practical Zn metal batteries enabled by the Zn(TFSI)2-mediated electrolyte engineering.展开更多
Featuring low cost, high abundance, low electrochemical potential, and large specific capacity, zinc(Zn)metal holds great potential as an anode material for next-generation rechargeable aqueous batteries.However, the ...Featuring low cost, high abundance, low electrochemical potential, and large specific capacity, zinc(Zn)metal holds great potential as an anode material for next-generation rechargeable aqueous batteries.However, the poor reversibility resulting from dendrite formation and side reactions poses a major obstacle for its practical application. Electrolyte, which is regarded as the “blood” of batteries, has a direct impact on reaction kinetics, mass transport, and side reactions and thus plays a key role in determining the electrochemical performance of Zn electrodes. Therefore, considerable efforts have been devoted to modulating the electrolytes to improve the performance of Zn electrodes. Although significant progress has been made, achieving stable and highly reversible Zn electrodes remains a critical challenge. This review aims to provide a systematic summary and discussion on electrolyte strategies for highperformance aqueous Zn batteries. The(electro)-chemical behavior and fundamental challenges of Zn electrodes in aqueous electrolytes are first discussed. Electrolyte modulation strategies developed to address these issues are then classified and elaborated according to the underlying mechanisms.Finally, remaining challenges and promising future research directions on aqueous electrolyte engineering are highlighted. This review offers insights into the design of highly efficient electrolytes for new generation of rechargeable Zn batteries.展开更多
Aqueous electrochemical energy storage(EES)devices are highly safe,environmentally benign,and inexpensive,but their operating voltage and energy density must be increased if they are to efficiently power multifunction...Aqueous electrochemical energy storage(EES)devices are highly safe,environmentally benign,and inexpensive,but their operating voltage and energy density must be increased if they are to efficiently power multifunctional electronics,new-energy cars as well as to be used in smart grids.This Minireview summarizes the key breakthroughs and progress in expanding the electrochemical stability window(ESW)of aqueous EES devices over the past five years.After briefly introducing the electrode engineering ways to widen ESW,we focus on four ground-breaking electrolyte engineering strategies and classify them into two kinds from the perspective of salts and exotic solutes/solvents.The widening degree toward ESW of these emerging electrolytes is compared and the universal fundamental mechanism relating to the interactions between limited water molecules and high-concentration salts(or large amounts of exotic solutes/solvents)is elucidated.Key challenges and perspectives for high-ESW electrolytes as well as recent advances in low-cost and other metal ion(sodium,potassium,zinc,etc.)-based electrolytes for expanding ESW are also outlined.展开更多
Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrit...Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrite growth,hydrogen evolution reaction,and interfacial passivation occurring at the anode/electrolyte interface(AEI) have hindered their practical application.Constructing a stable AEI plays a key role in regulating zinc deposition and improving the cycle life of AZIBs.The fundamentals of AEI and the challenges faced by the Zn anode due to unstable interfaces are discussed.A comprehensive summary of electrolyte regulation strategies by electrolyte engineering to achieve a stable Zn anode is provided.The effectiveness evaluation techniques for stable AEI are also analyzed,including the interfacial chemistry and surface morphology evolution of the Zn anode.Finally,suggestions and perspectives for future research are offered about enabling a durable and stable AEI via electrolyte engineering,which may pave the way for developing high-performance AZIBs.展开更多
Aqueous rechargeable batteries are safe and environmentally friendly and can be made at a low cost;as such,they are attracting attention in the field of energy storage.However,the temperature sensitivity of aqueous ba...Aqueous rechargeable batteries are safe and environmentally friendly and can be made at a low cost;as such,they are attracting attention in the field of energy storage.However,the temperature sensitivity of aqueous batteries hinders their practical application.The solvent water freezes at low temperatures,and there is a reduction in ionic conductivity,whereas it evaporates rapidly at high temperatures,which causes increased side reactions.This review discusses recent progress in improving the performance of aqueous batteries,mainly with respect to electrolyte engineering and the associated strategies employed to achieve such improvements over a wide temperature domain.The review focuses on fi ve electrolyte engineer-ing(aqueous high-concentration electrolytes,organic electrolytes,quasi-solid/solid electrolytes,hybrid electrolytes,and eutectic electrolytes)and investigates the mechanisms involved in reducing the solidifi cation point and boiling point of the electrolyte and enhancing the extreme-temperature electrochemical performance.Finally,the prospect of further improving the wide temperature range performance of aqueous rechargeable batteries is presented.展开更多
The pursuit of high-energy-density lithium-ion batteries has driven the development of high-voltage cathodes such as LiCoO2(LCO)[1].However,cycling beyond 4.5 V(vs.Li/Li+),especially at elevated temperatures,introduce...The pursuit of high-energy-density lithium-ion batteries has driven the development of high-voltage cathodes such as LiCoO2(LCO)[1].However,cycling beyond 4.5 V(vs.Li/Li+),especially at elevated temperatures,introduces severe challenges of accelerated interfacial side reactions,e.g.,dissolution of the cathode electrolyte interphase(CEI)and transition metal ions[2,3].Conventional carbonate-based electrolytes form CEI layers rich in organic components with poor thermal and electrochemical stability,which leads to rapid capacity fade,gas evolution,and safety hazards,thereby putting rigorous requirements on deliberate electrolyte design[4,5].展开更多
High-nickel cathode LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)could enable lithium-ion batteries(LIBs)with high energy density.However,excessive decomposition of the electrolyte would happen in the high operating voltage...High-nickel cathode LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)could enable lithium-ion batteries(LIBs)with high energy density.However,excessive decomposition of the electrolyte would happen in the high operating voltage range.In addition,the utilization of flammable organic solvents would increase safety risks in the high temperature environment.Herein,an electrolyte consisting of flame-retardant solvents with lower highest occupied molecular orbital(HOMO)level and LiDFOB salt is proposed to address above two issues.As a result,a thin and robust cathode-electrolyte interface containing rich LiF and Li-B-O compounds is formed on the cathode to effectively suppress electrolyte decomposition in the high operating voltage.The NCM811||Li cell paired with this designed electrolyte possesses a capacity retention of 72%after 300 cycles at 55℃.This work provides insights into developing electrolyte for stable high-nickel cathode operated in the high temperature.展开更多
The growing severity of environmental challenges has accelerated advancements in renewable energy technologies,highlighting the critical need for efficient energy storage solutions.Rechargeable batteries,as primary sh...The growing severity of environmental challenges has accelerated advancements in renewable energy technologies,highlighting the critical need for efficient energy storage solutions.Rechargeable batteries,as primary short-term energy storage devices,have seen significant progress.Among emerging optimization strategies,high-entropy electrolytes have garnered attention for their superior ionic conductivity and ability to broaden batteries’operational temperature ranges.Rooted in the thermodynamic concept of entropy,high-entropy materials,originally exemplified by high-entropy alloys,have demonstrated enhanced structural stability and advanced electrochemical performance through the synergistic integration of multiple components.High-entropy liquid electrolytes,both aqueous and non-aqueous,offer unique opportunities for entropy manipulation due to their inherently disordered structures.However,their complex compositions present challenges,as minor changes in formulation can lead to significant performance variations.This review introduces the fundamentals of entropy tuning,surveys recent advances in high-entropy liquid electrolytes,and analyzes the interplay between entropy and electrochemical behavior.Finally,it discusses design strategies and future perspectives for the practical implementation of high-entropy liquid electrolytes in next-generation energy storage systems.展开更多
Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents...Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents,a systematic understanding of how fluorination patterns impact electrolyte performance is still lacking.We investigate the effects of fluorination patterns on properties of electrolytes using fluorinated 1,2-diethoxyethane(FDEE)as single solvents.By employing quantum calculations,molecular dynamics simulations,and interpretable machine learning,we establish significant correlations between fluorination patterns and electrolyte properties.Higher fluorination levels enhance FDEE stability but decrease conductivity.The symmetry of fluorination sites is critical for stability and viscosity,while exerting minimal influence on ionic conductivity.FDEEs with highly symmetric fluorination sites exhibit favorable viscosity,stability,and overall electrolyte performance.Conductivity primarily depends on lithium-anion dissociation or association.These findings provide design principles for rational fluoroether electrolyte design,emphasizing the trade-offs between stability,viscosity,and conductivity.Our work underscores the significance of considering fluorination patterns and molecular symmetry in the development of fluoroether-based electrolytes for advanced lithium batteries.展开更多
Zn-based aqueous batteries(ZABs) are gaining widespread popularity due to their low cost and high safety profile. However, the application of ZABs faces significant challenges, such as dendrite growth and parasitic re...Zn-based aqueous batteries(ZABs) are gaining widespread popularity due to their low cost and high safety profile. However, the application of ZABs faces significant challenges, such as dendrite growth and parasitic reactions of metallic Zn anodes. Therefore, achieving high-energy–density ZABs necessitates addressing the fundamental thermodynamics and kinetics of Zn anodes. Various strategies are available to mitigate these challenges, with electrolyte additive engineering emerging as one of the most efficient and promising approaches. Despite considerable research in this field, a comprehensive understanding of the intrinsic mechanisms behind the high performance of electrolyte additives remains limited. This review aims to provide a detailed introduction to functional electrolyte additives and thoroughly explore their underlying mechanisms. Additionally, it discusses potential directions and perspectives in additive engineering for ZABs, offering insights into future development and guidelines for achieving high-performance ZABs.展开更多
With the merits of the high energy density of batteries and power density of supercapacitors,the aqueous Zn-ion hybrid supercapacitors emerge as a promising candidate for applications where both rapid energy delivery ...With the merits of the high energy density of batteries and power density of supercapacitors,the aqueous Zn-ion hybrid supercapacitors emerge as a promising candidate for applications where both rapid energy delivery and moderate energy storage are required.However,the narrow electrochemical window of aqueous electrolytes induces severe side reactions on the Zn metal anode and shortens its lifespan.It also limits the operation voltage and energy density of the Zn-ion hybrid supercapacitors.Using'water in salt'electrolytes can effectively broaden their electrochemical windows,but this is at the expense of high cost,low ionic conductivity,and narrow temperature compatibility,compromising the electrochemical performance of the Zn-ion hybrid supercapacitors.Thus,designing a new electrolyte to balance these factors towards high-performance Zn-ion hybrid supercapacitors is urgent and necessary.We developed a dilute water/acetonitrile electrolyte(0.5 m Zn(CF_(3)SO_(3))_(2)+1 m LiTFSI-H_(2)O/AN)for Zn-ion hybrid supercapacitors,which simultaneously exhibited expanded electrochemical window,decent ionic conductivity,and broad temperature compatibility.In this electrolyte,the hydration shells and hydrogen bonds are significantly modulated by the acetonitrile and TFSI-anions.As a result,a Zn-ion hybrid supercapacitor with such an electrolyte demonstrates a high operating voltage up to 2.2 V and long lifespan beyond 120,000 cycles.展开更多
Mg-air batteries have attracted tremendous attention as a potential next-generation power source for portable electronics and e-transportation due to their remarkable high theoretical volumetric energy density,environ...Mg-air batteries have attracted tremendous attention as a potential next-generation power source for portable electronics and e-transportation due to their remarkable high theoretical volumetric energy density,environmental sustainability,and cost-effectiveness.However,the fast hydrogen evolution reaction(HER)in NaCl-based aqueous electrolytes impairs the performance of Mg-air batteries and leads to poor specific capacity,low energy density,and low utilization.Thus,the conventionally used NaCl solute was proposed to be replaced by NaNO_(3)and acetic acid additive as a corrosion inhibitor,therefore an electrolyte engineering for long-life time Mg-air batteries is reported.The resulting Mg-air batteries based on this optimized electrolyte demonstrate an improved discharge voltage reaching~1.8 V for initial 5 h at a current density of 0.5 mA/cm^(2) and significantly prolonged cells'operational lifetime to over 360 h,in contrast to only~17 h observed in NaCl electrolyte.X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry were employed to analyse the composition of surface film and scanning electron microscopy combined with transmission electron microscopy to clarify the morphology changes of the surface layer as a function of acetic acid addition.The thorough studies of chemical composition and morphology of corrosion products have allowed us to elucidate the working mechanism of Mg anode in this optimized electrolyte for Mg-air batteries.展开更多
Cu-Li battery with Cu metal cathode and Li metal anode is a candidate for next-generation energy storage system.While self-discharge of the battery can be suppressed with an anion exchange membrane,the voltage polariz...Cu-Li battery with Cu metal cathode and Li metal anode is a candidate for next-generation energy storage system.While self-discharge of the battery can be suppressed with an anion exchange membrane,the voltage polarization depends strongly on the electrolyte.Specifically,when an electrolyte with 3 M LiTFSI(lithium bis(trifluoromethanesulfonyl)imide)in dimethyl carbonate(DMC)is used,overpotential increases with cycling.In this work,we reveal why the voltage polarization changes,and reduce and stabilize it by replacing DMC solvent with a mixed solvent composed of dimethoxyethane(DME)and propylene carbonate(PC).The new electrolyte has higher ionic conductivity and stable solvation structure with more free TFSI-anions upon cycling,which also facilitates uniform plating of metal ions on the metal electrodes.These characteristics enable a stable Cu-Li battery with minimal change in overpotential for more than 1500 cycles at a current density of 2 m A cm^(-2).展开更多
As the application of next-generation energy storage systems continues to expand,rechargeable secondary batteries with enhanced energy density and safety are imperative for energy iteration.Sodium-ion batteries(SIBs)h...As the application of next-generation energy storage systems continues to expand,rechargeable secondary batteries with enhanced energy density and safety are imperative for energy iteration.Sodium-ion batteries(SIBs)have attracted extensive attention and are recognized as ideal candidates for large-scale energy storage due to the abundant sodium resources and low cost.Sodium metal anodes(SMAs)have been considered as one of the most attractive anode materials for SIBs owing to their high specific capacity(1166 mAh g^(-1)),low redox potential,and abundant natural resources.However,the uncontrollable dendrite growth and inevitable side reactions on SMA lead to the continuous deterioration of the electrochemical performance,causing serious safety concerns and limiting their practical application in the future.Therefore,the construction of stable dendrite-free SMAs is a pressing problem for advanced sodium metal batteries(SMBs).In this review,we comprehensively summarize the research progress in suppressing the formation of sodium dendrite,including artificial solid electrolyte interphase(SEI),liquid electrolyte modification,three-dimensional(3D)host materials,and solid-state electrolyte.Additionally,key aspects and prospects of future research directions for SMAs are highlighted.We hope that this timely review can provide an overall picture of sodium protection strategies and stimulate more research in the future.展开更多
With the low cost,excellent safety and high theoretical specific capacity,aqueous zinc-ion batteries(AZ-IBs)are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large...With the low cost,excellent safety and high theoretical specific capacity,aqueous zinc-ion batteries(AZ-IBs)are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large-scale energy storage technologies.However,the notorious Zn dendrites and low Coulombic effi-ciency(CE)limit further development of AZIBs,due to the unstable electrochemical deposition/stripping behavior of Zn anode in aqueous zinc ion electrolytes.In this review,critical issues and advances are summarized in electrolyte engineering strategies.These strategies are focused on active water molecules during electrochemical process,including high-concentration electrolytes,ionic liquids,gel-polymer elec-trolytes and functional additives.With suppressed active water molecules,the solvation and de-solvation behavior of Zn^(2+)can be regulated,thereby modulating the electrochemical performance of Zn anode.Finally,the inherent problems of these strategies are discussed,and some promising directions are pro-vided on electrolytes engineering for high performance Zn anode in AZIBs.展开更多
Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose...Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose a general descriptor,the CO_(2)activity,to reveal the electrolyte–electrode-reaction relationship by thermodynamic calculations and experimental studies.Experimental studies agree well with theoretical predictions that both cations(Li^(+),Ca^(2+),Sr^(2+)and Ba^(2+))and anions(BO_(2)^(-),Ti_(5)O_(14)^(8-),SiO_(3)^(2-))can modulate the CO_(2)activity to control both cathode and anode reactions in a typical molten carbonate electrolyzer in terms of tuning reaction products and overpotentials.In this regard,the reduction of CO_(3)^(2-)can be interpreted as the direct reduction of CO_(2)generated from the dissociated CO_(3)^(2-),and the CO_(2)activity can be used as a general descriptor to predict the electrode reaction in molten carbonate.Overall,the CO_(2)activity descriptor unlocks the electrolyte–electrode-reaction relationship,thereby providing fundamental insights into guiding molten carbonate CO_(2)electrolysis.展开更多
Lithium metal batteries(LMBs)have gained increasing attention owing to high energy density for large-scale energy storage applications.However,serious side reactions between Li anodes and organic electrolytes lead to ...Lithium metal batteries(LMBs)have gained increasing attention owing to high energy density for large-scale energy storage applications.However,serious side reactions between Li anodes and organic electrolytes lead to low Columbic efficiency and Li dendrites.Although progress has been achieved in constructing electrode structures,the interfacial instability of Li anodes is still challenging.Solvation chemistry significantly affects the electrolyte properties and interfacial reactions,but the reaction mechanisms and the roles of each component in electrolytes are still vague.This review spotlights the recent development of electrolyte regulation with concentration and composition adjustments,aiming to understanding the correlation between solvation structures and Li anode stability.Further perspectives on the solvation design are provided in light of anode interfacial stability in LMBs.展开更多
Lithiummetal batteries(LMBs)offer high theoretical capacity and low redox potential,making them attractive for next-generation energy storage.However,their practical application is limited by dendrite formation,interf...Lithiummetal batteries(LMBs)offer high theoretical capacity and low redox potential,making them attractive for next-generation energy storage.However,their practical application is limited by dendrite formation,interfacial instability,parasitic reactions,and poor long-term cycling under realistic conditions.Recent advances suggest that supramolecular chemistry offers a powerful and modular framework for addressing these limitations via controlled molecular-level interactions.In this review,we highlight how supramolecular self-assembly strategies enable precise manipulation of liquid electrolyte structure,interfacial composition,and bulk solid-state architecture.We first discuss self-assembly in liquid electrolytes,where supramolecular interactions regulate lithium-ion solvation and promote dynamic interfacial passivation.We then analyze the role of supramolecular layers at different interfaces in batteries,both spontaneously formed and artificially engineered,for constructing robust and adaptive interphases.Finally,we examine bulk solid-state electrolytes,in which directional supramolecular interactions facilitate ion transport and mechanical integrity.Across these domains,supramolecular self-assembly emerges as a unifying strategy that transforms the electrolyte and interphase from passive components into actively engineered systems.This approach not only enables dynamic interfacial regulation and improved cycling stability but also opens new avenues for themolecular design of highperformance and durable LMBs.展开更多
Rechargeable room-temperature sodium–sulfur(Na–S)and sodium–selenium(Na–Se)batteries are gaining extensive attention for potential large-scale energy storage applications owing to their low cost and high theoretic...Rechargeable room-temperature sodium–sulfur(Na–S)and sodium–selenium(Na–Se)batteries are gaining extensive attention for potential large-scale energy storage applications owing to their low cost and high theoretical energy density.Optimization of electrode materials and investigation of mechanisms are essential to achieve high energy density and long-term cycling stability of Na–S(Se)batteries.Herein,we provide a comprehensive review of the recent progress in Na–S(Se)batteries.We elucidate the Na storage mechanisms and improvement strategies for battery performance.In particular,we discuss the advances in the development of battery components,including high-performance sulfur cathodes,optimized electrolytes,advanced Na metal anodes and modified separators.Combined with current research achievements,this review outlines remaining challenges and clear research directions for the future development of practical high-performance Na–S(Se)batteries.展开更多
The unstable zinc anode/electrolyte interface induced by corrosion,interfacial water splitting reaction,and dendrite growth seriously degrades the performances of metal Zn anode in aqueous electrolyte.Herein,the nucle...The unstable zinc anode/electrolyte interface induced by corrosion,interfacial water splitting reaction,and dendrite growth seriously degrades the performances of metal Zn anode in aqueous electrolyte.Herein,the nucleation and growth of zinc hydroxide sulfate(ZHS),an interfacial by-product,has been tailored by Tween 80 in the electrolyte,which thereby assists in in-situ forming a dense solid electrolyte interphase(SEI)with small-sized ZHS and evenly distributed Tween 80.This SEI has high corrosion resistance and uniform distribution of zinc ions,which not only contributes to blocking the interfacial side reactions but also induces stable and calm zinc plating/stripping.Consequently,the modified electrolyte can confer the assembled Zn||Zn symmetric cell with a stable operation life over 1500 h at 1 mA·cm^(−2)and 1 mAh·cm^(−2)as well as the practical Zn||NH4V4O10 full battery with a high-rate capacity of 120 mAh·g^(−1)at the current density of 5 A·g^(−1).This work provides a way for regulating and reusing interfacial by-products,and a new sight on stabilization electrodes/electrolyte interfaces.展开更多
基金financially supported by the National Natural Science Foundation of China(52162036 and 22378342)Key Project of Nature Science Foundation of Xinjiang(2021D01D08)+2 种基金Major Projects of Xinjiang(2022A01005-4 and 2021A01001-1)Key Research and Development Project of Xinjiang(2023B01025-1)the support from the Doctoral Student Special Program of the Young Talents Support Project of the China Association for Science and Technology in 2024。
文摘Practical Zn metal batteries have been hindered by several challenges,including Zn dendrite growth,undesirable side reactions,and unstable electrode/electrolyte interface.These issues are particularly more serious in low-concentration electrolytes.Herein,we design a Zn salt-mediated electrolyte with in situ ring-opening polymerization of the small molecule organic solvent.The Zn(TFSI)_(2)salt catalyzes the ring-opening polymerization of(1,3-dioxolane(DOL)),generating oxidation-resistant and non-combustible long-chain polymer(poly(1,3-dioxolane)(pDOL)).The pDOL reduces the active H_(2)O molecules in electrolyte and assists in forming stable organic–inorganic gradient solid electrolyte interphase with rich organic constituents,ZnO and ZnF_(2).The introduction of pDOL endows the electrolyte with several advantages:excellent Zn dendrite inhibition,improved corrosion resistance,widened electrochemical window(2.6 V),and enhanced low-temperature performance(freezing point=-34.9°C).Zn plating/stripping in pDOL-enhanced electrolyte lasts for 4200 cycles at 99.02%Coulomb efficiency and maintains a lifetime of 8200 h.Moreover,Zn metal anodes deliver stable cycling for 2500 h with a high Zn utilization of 60%.A Zn//VO_(2)pouch cell assembled with lean electrolyte(electrolyte/capacity(E/C=41 mL(Ah)^(-1))also demonstrates a capacity retention ratio of 92%after 600 cycles.These results highlight the promising application prospects of practical Zn metal batteries enabled by the Zn(TFSI)2-mediated electrolyte engineering.
文摘Featuring low cost, high abundance, low electrochemical potential, and large specific capacity, zinc(Zn)metal holds great potential as an anode material for next-generation rechargeable aqueous batteries.However, the poor reversibility resulting from dendrite formation and side reactions poses a major obstacle for its practical application. Electrolyte, which is regarded as the “blood” of batteries, has a direct impact on reaction kinetics, mass transport, and side reactions and thus plays a key role in determining the electrochemical performance of Zn electrodes. Therefore, considerable efforts have been devoted to modulating the electrolytes to improve the performance of Zn electrodes. Although significant progress has been made, achieving stable and highly reversible Zn electrodes remains a critical challenge. This review aims to provide a systematic summary and discussion on electrolyte strategies for highperformance aqueous Zn batteries. The(electro)-chemical behavior and fundamental challenges of Zn electrodes in aqueous electrolytes are first discussed. Electrolyte modulation strategies developed to address these issues are then classified and elaborated according to the underlying mechanisms.Finally, remaining challenges and promising future research directions on aqueous electrolyte engineering are highlighted. This review offers insights into the design of highly efficient electrolytes for new generation of rechargeable Zn batteries.
基金supported by grants from the National Natural Science Foundation of China(Grant Nos.51972257,51872104 and 51672205)the National Key R&D Program of China(Grant No.2016YFA0202602)the Natural Science Foundation of Hubei Province(2018CFB581)
文摘Aqueous electrochemical energy storage(EES)devices are highly safe,environmentally benign,and inexpensive,but their operating voltage and energy density must be increased if they are to efficiently power multifunctional electronics,new-energy cars as well as to be used in smart grids.This Minireview summarizes the key breakthroughs and progress in expanding the electrochemical stability window(ESW)of aqueous EES devices over the past five years.After briefly introducing the electrode engineering ways to widen ESW,we focus on four ground-breaking electrolyte engineering strategies and classify them into two kinds from the perspective of salts and exotic solutes/solvents.The widening degree toward ESW of these emerging electrolytes is compared and the universal fundamental mechanism relating to the interactions between limited water molecules and high-concentration salts(or large amounts of exotic solutes/solvents)is elucidated.Key challenges and perspectives for high-ESW electrolytes as well as recent advances in low-cost and other metal ion(sodium,potassium,zinc,etc.)-based electrolytes for expanding ESW are also outlined.
基金financially supported by the National Natural Science Foundation of China (No. 52377222)the Natural Science Foundation of Hunan Province, China (Nos. 2023JJ20064, 2023JJ40759)。
文摘Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrite growth,hydrogen evolution reaction,and interfacial passivation occurring at the anode/electrolyte interface(AEI) have hindered their practical application.Constructing a stable AEI plays a key role in regulating zinc deposition and improving the cycle life of AZIBs.The fundamentals of AEI and the challenges faced by the Zn anode due to unstable interfaces are discussed.A comprehensive summary of electrolyte regulation strategies by electrolyte engineering to achieve a stable Zn anode is provided.The effectiveness evaluation techniques for stable AEI are also analyzed,including the interfacial chemistry and surface morphology evolution of the Zn anode.Finally,suggestions and perspectives for future research are offered about enabling a durable and stable AEI via electrolyte engineering,which may pave the way for developing high-performance AZIBs.
基金supported by the National Key Research and Development Program of China(2019YFC1904500)National Natural Science Foundation of China(Nos.21801251,51502036,and 21875037)+2 种基金Young Top Talent of Fujian Young Eagle Program of Fujian Province,Educational Commis-sion of Fujian Province(2022G02022)Natural Science Foundation of Fuzhou City(2022-Y-004)Natural Science Foundation of Fujian Province(2023J02013).
文摘Aqueous rechargeable batteries are safe and environmentally friendly and can be made at a low cost;as such,they are attracting attention in the field of energy storage.However,the temperature sensitivity of aqueous batteries hinders their practical application.The solvent water freezes at low temperatures,and there is a reduction in ionic conductivity,whereas it evaporates rapidly at high temperatures,which causes increased side reactions.This review discusses recent progress in improving the performance of aqueous batteries,mainly with respect to electrolyte engineering and the associated strategies employed to achieve such improvements over a wide temperature domain.The review focuses on fi ve electrolyte engineer-ing(aqueous high-concentration electrolytes,organic electrolytes,quasi-solid/solid electrolytes,hybrid electrolytes,and eutectic electrolytes)and investigates the mechanisms involved in reducing the solidifi cation point and boiling point of the electrolyte and enhancing the extreme-temperature electrochemical performance.Finally,the prospect of further improving the wide temperature range performance of aqueous rechargeable batteries is presented.
文摘The pursuit of high-energy-density lithium-ion batteries has driven the development of high-voltage cathodes such as LiCoO2(LCO)[1].However,cycling beyond 4.5 V(vs.Li/Li+),especially at elevated temperatures,introduces severe challenges of accelerated interfacial side reactions,e.g.,dissolution of the cathode electrolyte interphase(CEI)and transition metal ions[2,3].Conventional carbonate-based electrolytes form CEI layers rich in organic components with poor thermal and electrochemical stability,which leads to rapid capacity fade,gas evolution,and safety hazards,thereby putting rigorous requirements on deliberate electrolyte design[4,5].
基金supported by the National Key Research and Development Program of China(2022YFB3803400)。
文摘High-nickel cathode LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)could enable lithium-ion batteries(LIBs)with high energy density.However,excessive decomposition of the electrolyte would happen in the high operating voltage range.In addition,the utilization of flammable organic solvents would increase safety risks in the high temperature environment.Herein,an electrolyte consisting of flame-retardant solvents with lower highest occupied molecular orbital(HOMO)level and LiDFOB salt is proposed to address above two issues.As a result,a thin and robust cathode-electrolyte interface containing rich LiF and Li-B-O compounds is formed on the cathode to effectively suppress electrolyte decomposition in the high operating voltage.The NCM811||Li cell paired with this designed electrolyte possesses a capacity retention of 72%after 300 cycles at 55℃.This work provides insights into developing electrolyte for stable high-nickel cathode operated in the high temperature.
基金supported by a grant from the Research Grants Council of the Hong Kong Special Administrative Region,China(N_PolyU559/21)a grant from the National Natural Science Foundation of China(52161160333)+1 种基金a grant from the Research Institute for Smart Energy at The Hong Kong Polytechnic University(CDB2)supported by the Hong Kong PhD Fellowship Scheme(PF21-65328).
文摘The growing severity of environmental challenges has accelerated advancements in renewable energy technologies,highlighting the critical need for efficient energy storage solutions.Rechargeable batteries,as primary short-term energy storage devices,have seen significant progress.Among emerging optimization strategies,high-entropy electrolytes have garnered attention for their superior ionic conductivity and ability to broaden batteries’operational temperature ranges.Rooted in the thermodynamic concept of entropy,high-entropy materials,originally exemplified by high-entropy alloys,have demonstrated enhanced structural stability and advanced electrochemical performance through the synergistic integration of multiple components.High-entropy liquid electrolytes,both aqueous and non-aqueous,offer unique opportunities for entropy manipulation due to their inherently disordered structures.However,their complex compositions present challenges,as minor changes in formulation can lead to significant performance variations.This review introduces the fundamentals of entropy tuning,surveys recent advances in high-entropy liquid electrolytes,and analyzes the interplay between entropy and electrochemical behavior.Finally,it discusses design strategies and future perspectives for the practical implementation of high-entropy liquid electrolytes in next-generation energy storage systems.
基金supported by the Major Research Plan of the National Natural Science Foundation of China(92372104)Guangdong Basic and Applied Basic Research Foundation(2022A1515110016)+3 种基金the Recruitment Program of Guangdong(2016ZT06C322)R&D Program of Guangzhou(2023A04J1364)Fundamental Research Funds for the Central Universities(2024ZYGXZR043)TCL Science and Technology Innovation Fund。
文摘Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents,a systematic understanding of how fluorination patterns impact electrolyte performance is still lacking.We investigate the effects of fluorination patterns on properties of electrolytes using fluorinated 1,2-diethoxyethane(FDEE)as single solvents.By employing quantum calculations,molecular dynamics simulations,and interpretable machine learning,we establish significant correlations between fluorination patterns and electrolyte properties.Higher fluorination levels enhance FDEE stability but decrease conductivity.The symmetry of fluorination sites is critical for stability and viscosity,while exerting minimal influence on ionic conductivity.FDEEs with highly symmetric fluorination sites exhibit favorable viscosity,stability,and overall electrolyte performance.Conductivity primarily depends on lithium-anion dissociation or association.These findings provide design principles for rational fluoroether electrolyte design,emphasizing the trade-offs between stability,viscosity,and conductivity.Our work underscores the significance of considering fluorination patterns and molecular symmetry in the development of fluoroether-based electrolytes for advanced lithium batteries.
基金financially National Natural Science Foundation of China (22309165)Excellent Youth Foundation of Henan Province (242300421126)+6 种基金Talent Development Funding Project of Shanghai (2021030)Joint Fund of Science and Technology R&D Plan of Henan Province (232301420053)Postdoctoral Science Foundation of China (2023M743170)Key Research Projects of Higher Education Institutions of Henan Province (24A530010, and 23A530002)Key Laboratory of Adv. Mater. of Ministry of Education (Adv Mat2023-17)State Key Laboratory of Inorganic Synthesis & Preparative Chemistry Jilin University (2024-34)Frontier Exploration Projects of Longmen Laboratory of Henan (LMQYTSKT021)。
文摘Zn-based aqueous batteries(ZABs) are gaining widespread popularity due to their low cost and high safety profile. However, the application of ZABs faces significant challenges, such as dendrite growth and parasitic reactions of metallic Zn anodes. Therefore, achieving high-energy–density ZABs necessitates addressing the fundamental thermodynamics and kinetics of Zn anodes. Various strategies are available to mitigate these challenges, with electrolyte additive engineering emerging as one of the most efficient and promising approaches. Despite considerable research in this field, a comprehensive understanding of the intrinsic mechanisms behind the high performance of electrolyte additives remains limited. This review aims to provide a detailed introduction to functional electrolyte additives and thoroughly explore their underlying mechanisms. Additionally, it discusses potential directions and perspectives in additive engineering for ZABs, offering insights into future development and guidelines for achieving high-performance ZABs.
基金supported by the National Nature Science Foundation of China(22209211 and 52172241)Hong Kong Research Grants Council(CityU 11315622)+1 种基金the research funds from South-Central Minzu University(YZZ22001)the National Key R&D Program of China(2021YFA1501101).
文摘With the merits of the high energy density of batteries and power density of supercapacitors,the aqueous Zn-ion hybrid supercapacitors emerge as a promising candidate for applications where both rapid energy delivery and moderate energy storage are required.However,the narrow electrochemical window of aqueous electrolytes induces severe side reactions on the Zn metal anode and shortens its lifespan.It also limits the operation voltage and energy density of the Zn-ion hybrid supercapacitors.Using'water in salt'electrolytes can effectively broaden their electrochemical windows,but this is at the expense of high cost,low ionic conductivity,and narrow temperature compatibility,compromising the electrochemical performance of the Zn-ion hybrid supercapacitors.Thus,designing a new electrolyte to balance these factors towards high-performance Zn-ion hybrid supercapacitors is urgent and necessary.We developed a dilute water/acetonitrile electrolyte(0.5 m Zn(CF_(3)SO_(3))_(2)+1 m LiTFSI-H_(2)O/AN)for Zn-ion hybrid supercapacitors,which simultaneously exhibited expanded electrochemical window,decent ionic conductivity,and broad temperature compatibility.In this electrolyte,the hydration shells and hydrogen bonds are significantly modulated by the acetonitrile and TFSI-anions.As a result,a Zn-ion hybrid supercapacitor with such an electrolyte demonstrates a high operating voltage up to 2.2 V and long lifespan beyond 120,000 cycles.
基金the China Scholarship Council(CSC)for funding(no.201806310116)。
文摘Mg-air batteries have attracted tremendous attention as a potential next-generation power source for portable electronics and e-transportation due to their remarkable high theoretical volumetric energy density,environmental sustainability,and cost-effectiveness.However,the fast hydrogen evolution reaction(HER)in NaCl-based aqueous electrolytes impairs the performance of Mg-air batteries and leads to poor specific capacity,low energy density,and low utilization.Thus,the conventionally used NaCl solute was proposed to be replaced by NaNO_(3)and acetic acid additive as a corrosion inhibitor,therefore an electrolyte engineering for long-life time Mg-air batteries is reported.The resulting Mg-air batteries based on this optimized electrolyte demonstrate an improved discharge voltage reaching~1.8 V for initial 5 h at a current density of 0.5 mA/cm^(2) and significantly prolonged cells'operational lifetime to over 360 h,in contrast to only~17 h observed in NaCl electrolyte.X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry were employed to analyse the composition of surface film and scanning electron microscopy combined with transmission electron microscopy to clarify the morphology changes of the surface layer as a function of acetic acid addition.The thorough studies of chemical composition and morphology of corrosion products have allowed us to elucidate the working mechanism of Mg anode in this optimized electrolyte for Mg-air batteries.
基金supported by a Research Matching Grant Scheme(PJ9229008)by the government of Hong Kong Special Administrative Region。
文摘Cu-Li battery with Cu metal cathode and Li metal anode is a candidate for next-generation energy storage system.While self-discharge of the battery can be suppressed with an anion exchange membrane,the voltage polarization depends strongly on the electrolyte.Specifically,when an electrolyte with 3 M LiTFSI(lithium bis(trifluoromethanesulfonyl)imide)in dimethyl carbonate(DMC)is used,overpotential increases with cycling.In this work,we reveal why the voltage polarization changes,and reduce and stabilize it by replacing DMC solvent with a mixed solvent composed of dimethoxyethane(DME)and propylene carbonate(PC).The new electrolyte has higher ionic conductivity and stable solvation structure with more free TFSI-anions upon cycling,which also facilitates uniform plating of metal ions on the metal electrodes.These characteristics enable a stable Cu-Li battery with minimal change in overpotential for more than 1500 cycles at a current density of 2 m A cm^(-2).
基金This study was supported by Beijing Natural Science Foundation(No.2202034)National Natural Science Foundation of China(No.21978024)the National Key R&D Program of China(No.2019YFB1309703)。
文摘As the application of next-generation energy storage systems continues to expand,rechargeable secondary batteries with enhanced energy density and safety are imperative for energy iteration.Sodium-ion batteries(SIBs)have attracted extensive attention and are recognized as ideal candidates for large-scale energy storage due to the abundant sodium resources and low cost.Sodium metal anodes(SMAs)have been considered as one of the most attractive anode materials for SIBs owing to their high specific capacity(1166 mAh g^(-1)),low redox potential,and abundant natural resources.However,the uncontrollable dendrite growth and inevitable side reactions on SMA lead to the continuous deterioration of the electrochemical performance,causing serious safety concerns and limiting their practical application in the future.Therefore,the construction of stable dendrite-free SMAs is a pressing problem for advanced sodium metal batteries(SMBs).In this review,we comprehensively summarize the research progress in suppressing the formation of sodium dendrite,including artificial solid electrolyte interphase(SEI),liquid electrolyte modification,three-dimensional(3D)host materials,and solid-state electrolyte.Additionally,key aspects and prospects of future research directions for SMAs are highlighted.We hope that this timely review can provide an overall picture of sodium protection strategies and stimulate more research in the future.
基金supported by the Science Fund for Natural Science Foundation of Hunan Province(No.2023JJ20064)the National Natural Science Foundation of China(No.52377222)Natural Science Foundation of Hunan Province(No.2023JJ50012).
文摘With the low cost,excellent safety and high theoretical specific capacity,aqueous zinc-ion batteries(AZ-IBs)are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large-scale energy storage technologies.However,the notorious Zn dendrites and low Coulombic effi-ciency(CE)limit further development of AZIBs,due to the unstable electrochemical deposition/stripping behavior of Zn anode in aqueous zinc ion electrolytes.In this review,critical issues and advances are summarized in electrolyte engineering strategies.These strategies are focused on active water molecules during electrochemical process,including high-concentration electrolytes,ionic liquids,gel-polymer elec-trolytes and functional additives.With suppressed active water molecules,the solvation and de-solvation behavior of Zn^(2+)can be regulated,thereby modulating the electrochemical performance of Zn anode.Finally,the inherent problems of these strategies are discussed,and some promising directions are pro-vided on electrolytes engineering for high performance Zn anode in AZIBs.
基金funded by National Natural Science Foun-dation of China(No.52031008,21673162).
文摘Molten carbonate is an excellent electrolyte for the electrochemical reduction of CO_(2)to carbonaceous materials.However,the electrolyte–electrode-reaction relationship has not been well understood.Herein,we propose a general descriptor,the CO_(2)activity,to reveal the electrolyte–electrode-reaction relationship by thermodynamic calculations and experimental studies.Experimental studies agree well with theoretical predictions that both cations(Li^(+),Ca^(2+),Sr^(2+)and Ba^(2+))and anions(BO_(2)^(-),Ti_(5)O_(14)^(8-),SiO_(3)^(2-))can modulate the CO_(2)activity to control both cathode and anode reactions in a typical molten carbonate electrolyzer in terms of tuning reaction products and overpotentials.In this regard,the reduction of CO_(3)^(2-)can be interpreted as the direct reduction of CO_(2)generated from the dissociated CO_(3)^(2-),and the CO_(2)activity can be used as a general descriptor to predict the electrode reaction in molten carbonate.Overall,the CO_(2)activity descriptor unlocks the electrolyte–electrode-reaction relationship,thereby providing fundamental insights into guiding molten carbonate CO_(2)electrolysis.
基金supported by the National Natural Science Foundation of China(No.52171215),the 111 project(No.B12015)Haihe Laboratory of Sustainable Chemical Transformations.
文摘Lithium metal batteries(LMBs)have gained increasing attention owing to high energy density for large-scale energy storage applications.However,serious side reactions between Li anodes and organic electrolytes lead to low Columbic efficiency and Li dendrites.Although progress has been achieved in constructing electrode structures,the interfacial instability of Li anodes is still challenging.Solvation chemistry significantly affects the electrolyte properties and interfacial reactions,but the reaction mechanisms and the roles of each component in electrolytes are still vague.This review spotlights the recent development of electrolyte regulation with concentration and composition adjustments,aiming to understanding the correlation between solvation structures and Li anode stability.Further perspectives on the solvation design are provided in light of anode interfacial stability in LMBs.
基金Tsinghua-Toyota Joint Research Fund and Tsinghua University-China Petrochemical Corporation Joint Institute for Green Chemical Engineering(224247).
文摘Lithiummetal batteries(LMBs)offer high theoretical capacity and low redox potential,making them attractive for next-generation energy storage.However,their practical application is limited by dendrite formation,interfacial instability,parasitic reactions,and poor long-term cycling under realistic conditions.Recent advances suggest that supramolecular chemistry offers a powerful and modular framework for addressing these limitations via controlled molecular-level interactions.In this review,we highlight how supramolecular self-assembly strategies enable precise manipulation of liquid electrolyte structure,interfacial composition,and bulk solid-state architecture.We first discuss self-assembly in liquid electrolytes,where supramolecular interactions regulate lithium-ion solvation and promote dynamic interfacial passivation.We then analyze the role of supramolecular layers at different interfaces in batteries,both spontaneously formed and artificially engineered,for constructing robust and adaptive interphases.Finally,we examine bulk solid-state electrolytes,in which directional supramolecular interactions facilitate ion transport and mechanical integrity.Across these domains,supramolecular self-assembly emerges as a unifying strategy that transforms the electrolyte and interphase from passive components into actively engineered systems.This approach not only enables dynamic interfacial regulation and improved cycling stability but also opens new avenues for themolecular design of highperformance and durable LMBs.
基金financial support from the Australian Research Council(ARC)through the ARC Discovery projects(DP200101249,DP210101389)the ARC Research Hub for Integrated Energy Storage Solutions(IH180100020).
文摘Rechargeable room-temperature sodium–sulfur(Na–S)and sodium–selenium(Na–Se)batteries are gaining extensive attention for potential large-scale energy storage applications owing to their low cost and high theoretical energy density.Optimization of electrode materials and investigation of mechanisms are essential to achieve high energy density and long-term cycling stability of Na–S(Se)batteries.Herein,we provide a comprehensive review of the recent progress in Na–S(Se)batteries.We elucidate the Na storage mechanisms and improvement strategies for battery performance.In particular,we discuss the advances in the development of battery components,including high-performance sulfur cathodes,optimized electrolytes,advanced Na metal anodes and modified separators.Combined with current research achievements,this review outlines remaining challenges and clear research directions for the future development of practical high-performance Na–S(Se)batteries.
基金the Material Corrosion and Protection Key Laboratory of Sichuan Province Support Program(No.2023CL02)the Yunnan Fundamental Research Projects(No.202201AU070151)the Innovation Fund of Postgraduate,Sichuan University of Science&Engineering(No.Y2022010).
文摘The unstable zinc anode/electrolyte interface induced by corrosion,interfacial water splitting reaction,and dendrite growth seriously degrades the performances of metal Zn anode in aqueous electrolyte.Herein,the nucleation and growth of zinc hydroxide sulfate(ZHS),an interfacial by-product,has been tailored by Tween 80 in the electrolyte,which thereby assists in in-situ forming a dense solid electrolyte interphase(SEI)with small-sized ZHS and evenly distributed Tween 80.This SEI has high corrosion resistance and uniform distribution of zinc ions,which not only contributes to blocking the interfacial side reactions but also induces stable and calm zinc plating/stripping.Consequently,the modified electrolyte can confer the assembled Zn||Zn symmetric cell with a stable operation life over 1500 h at 1 mA·cm^(−2)and 1 mAh·cm^(−2)as well as the practical Zn||NH4V4O10 full battery with a high-rate capacity of 120 mAh·g^(−1)at the current density of 5 A·g^(−1).This work provides a way for regulating and reusing interfacial by-products,and a new sight on stabilization electrodes/electrolyte interfaces.
