Rechargeable magnesium batteries(RMBs),as a low-cost,high-safety and high-energy storage technology,have attracted tremendous attention in large-scale energy storage applications.However,the key anode/electrolyte inte...Rechargeable magnesium batteries(RMBs),as a low-cost,high-safety and high-energy storage technology,have attracted tremendous attention in large-scale energy storage applications.However,the key anode/electrolyte interfacial issues,including surface passivation,uneven Mg plating/stripping,and pulverization after cycling still result in a large overpotential,short cycling life,poor power density,and possible safety hazards of cells,severely impeding the commercial development of RMBs.In this review,a concise overview of recently advanced strategies to address these anode/electroyte interfacial issues is systematically classified and summarized.The design of magnesiophilic substrates,construction of artificial SEI layers,and modification of electrolyte are important and effective strategies to improve the uniformity/kinetics of Mg plating/stripping and achieve the stable anode/electrolyte interface.The key opportunities and challenges in this field are advisedly put forward,and the insights into future directions for stabilizing Mg metal anodes and the anode/electrolyte interface are highlighted.This review provides important references fordeveloping the high-performance and high-safety RMBs.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 zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density...Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.展开更多
Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The ch...Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions.In this study,we have tuned orbital hybridization states forming an interface enriched with sp^(2) hybridized carbon(sp^(2)-C),which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation.Benefiting from successfully constructed inorganic-rich SEI,the ICE increased to 91%and sodium storage capacity reached 346 mAh/g.Besides,the capacity retention rate was 90.7%after 700 cycles at 1 A/g higher than pristine electrode(83.8%).展开更多
Aqueous-electrolyte-based zinc-ion batteries(ZIBs),which have significant advantages over other batteries,including low cost,high safety,high ionic conductivity,and a natural abundance of zinc,have been regarded as a ...Aqueous-electrolyte-based zinc-ion batteries(ZIBs),which have significant advantages over other batteries,including low cost,high safety,high ionic conductivity,and a natural abundance of zinc,have been regarded as a potential alternative to lithium-ion batteries(LIBs).ZIBs still face some critical challenges,however,especially for building a reversible zinc anode.To address the reversibility of zinc anode,great efforts have been made on intrinsic anode engineering and anode interface modification.Less attention has been devoted to the electrolyte additives,however,which could not only significantly improve the reversibility of zinc anode,but also determine the viability and overall performance of ZIBs.This review aims to provide an overview of the two main functions of electrolyte additives,followed by details on six reasons why additives might improve the performance of ZIBs from the perspectives of creating new layers and regulating current plating/stripping processes.Furthermore,the remaining difficulties and potential directions for additives in aqueous ZIBs are also highlighted.展开更多
The practical application of aqueous zinc-ion batteries(AZIBs)is primarily constrained by issues such as corrosion,zinc dendrite formation,and the hydrogen evolution reaction occurring at the zinc metal anode.To overc...The practical application of aqueous zinc-ion batteries(AZIBs)is primarily constrained by issues such as corrosion,zinc dendrite formation,and the hydrogen evolution reaction occurring at the zinc metal anode.To overcome these challenges,strategies for optimizing the electrolyte are crucial for enhancing the stability of the zinc anode.Inspired by the role of hemoglobin in blood cells,which facilitates oxygen transport during human respiration,an innovative inorganic colloidal electrolyte has been developed:calcium silicate-ZnSO_(4)(denoted as CS-ZSO).This electrolyte operates in weak acidic environment and releases calcium ions,which participate in homotopic substitution with zinc ions,while the solvation environment of hydrated zinc ions in the electrolyte is regulated.The reduced energy barrier for the transfer of zinc ions and the energy barrier for the desolvation of hydrated ions imply faster ion transfer kinetics and accelerated desolvation processes,thus favoring the mass transfer process.Furthermore,the silicate colloidal particles act as lubricants,improving the transfer of zinc ions.Together,these factors contribute to the more uniform concentration of zinc ions at the electrode/electrolyte interface,effectively inhibiting zinc dendrite formation and reducing by-product accumulation.The Zn//CS-ZSO//Zn symmetric cell demonstrates stable operation for over 5000 h at 1 mA cm^(-2),representing 29-fold improvement compared to the Zn//ZSO//Zn symmetric cell,which lasts only 170 h.Additionally,the Zn//CS-ZSO//Cu asymmetric cell shows stable average Coulombic efficiency(CE)exceeding 99.6%over2400 cycles,significantly surpassing the performance of the ZSO electrolyte.This modification strategy for electrolytes not only addresses key limitations associated with zinc anodes but also provides valuable insights into stabilizing anodes for the advancement of high-performance aqueous zinc-ion energy storage systems.展开更多
Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interf...Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of sodium-potassium(NaK)alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the physical contact of the electrode-electrolyte interface.Additionally,the filling of SiO_(2) nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 hrs.The full cell coupled with Na_(3)V_(2)(PO_(4))_(2) cathodes had an initial discharge capacity of 106.8 mAh·g^(-1) with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1) even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.展开更多
The development of lithium-ion batteries with high-energy densities is substantially hampered by the graphite anode's low theoretical capacity(372 mAh g^(-1)).There is an urgent need to explore novel anode materia...The development of lithium-ion batteries with high-energy densities is substantially hampered by the graphite anode's low theoretical capacity(372 mAh g^(-1)).There is an urgent need to explore novel anode materials for lithium-ion batteries.Silicon(Si),the second-largest element outside of Earth,has an exceptionally high specific capacity(3579 mAh g^(-1)),regarded as an excellent choice for the anode material in high-capacity lithium-ion batteries.However,it is low intrinsic conductivity and volume amplification during service status,prevented it from developing further.These difficulties can be successfully overcome by incorporating carbon into pure Si systems to form a composite anode and constructing a buffer structure.This review looks at the diffusion mechanism,various silicon-based anode material configurations(including sandwich,core-shell,yolk-shell,and other 3D mesh/porous structures),as well as the appropriate binders and electrolytes.Finally,a summary and viewpoints are offered on the characteristics and structural layout of various structures,metal/non-metal doping,and the compatibility and application of various binders and electrolytes for silicon-based anodes.This review aims to provide valuable insights into the research and development of silicon-based carbon anodes for high-performance lithium-ion batteries,as well as their integration with binders and electrolyte.展开更多
Aqueous zinc metal batteries have garnered substantial attention ascribing to affordability,intrinsic safety,and environmental benignity Nevertheless,zinc metal batteries yet are challenged with potential service life...Aqueous zinc metal batteries have garnered substantial attention ascribing to affordability,intrinsic safety,and environmental benignity Nevertheless,zinc metal batteries yet are challenged with potential service life issues resulted from dendrites and side reaction.In this paper,a strategy of nanoparticles doped hydrogel is proposed for constructing carboxymethyl cellulose/graphite oxide hybrid hydrogel electrolyte membranes with exceptional ionic conductivity,anti-swelling property,and simultaneously addressing the dendrites and parasitic reaction.The pivotal functions of the carboxymethyl cellulose/graphite oxide hydrogel electrolyte in mitigating hydrogen evolution and fostering accelerated Zn deposition have been elucidated based on principles of thermodynamic and reaction kinetic.The carboxymethyl cellulose/graphite oxide hydrogel electrolyte endows exceptional cycling longevity(800 h at 1 mA cm^(-2)/1 mAh cm^(-2))for Znjj Zn battery,as well as high Coulombic efficiency for Znjj Cu battery(averagely 99.14%within 439 cycles at 1 mA cm^(-2)/1 mAh cm^(-2)).The assembled Znjj NH_(4)V_(4)O_(10)battery delivers a high reversible specific capacity of 328.5 mAh g^(-1)at 0.1 A g^(-1).Moreover,the device of Znjj NH_(4)V_(4)O_(10)pouch battery remains operational under severe conditions like bending and cutting.This work provides valuable reference in developing inorganic nanoparticle hybrid hydrogel electrolyte for realizing high-performance zinc metal batteries.展开更多
Aqueous zinc-iodine(Zn-I_(2))batteries show great potential as energy storage candidates due to their high-safety and low-cost,but confronts hydrogen evolution reaction(HER)and dendrite growth at anode side and polyio...Aqueous zinc-iodine(Zn-I_(2))batteries show great potential as energy storage candidates due to their high-safety and low-cost,but confronts hydrogen evolution reaction(HER)and dendrite growth at anode side and polyiodide shuttling at cathode side.Herein,"tennis racket"(TR)hydrogel electrolytes were prepared by the co-polymerization and co-blending of polyacrylamide(PAM),sodium lignosulfonate(SL),and sodium alginate(SA)to synchronously regulate cathode and anode of Zn-I_(2)batteries."Gridline structure"of TR can induce the uniform transportation of Zn^(2+)ions through the coordination effect to hinder HER and dendrite growth at anode side,as well as hit I_(3)^(-)ions as"tennis"via the strong repulsion force to avoid shuttle effect at cathode side.The synergistic effect of TR electrolyte endows Zn-Zn symmetric battery with high cycling stability over 4500 h and Zn-I_(2)cell with the stably cycling life of 15000 cycles at5 A g^(-1),outperforming the reported works.The practicability of TR electrolyte is verified by flexible Zn-I_(2)pouch battery.This work opens a route to synchronously regulate cathode and anode to enhance the electrochemical performance of Zn-I_(2)batteries.展开更多
Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the sol...Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the solid-electrolyte interphase(SEI)during extended cycling use may result in dendrite growth,which can penetrate the separator and pose significant short-circuit risks.Forming a stable SEI is essential for the long-term operation of the batteries.Fluorine-rich SEI has garnered significant attention for its ability to effectively passivate electrodes,regulate lithium deposition,and inhibit electrolyte corrosion.Understanding the structural components and preparation methods of existing fluorinated SEI is crucial for optimizing lithium metal anode performance.This paper reviews the research on optimizing LiF passivation interfaces to protect lithium metal anodes.It focuses on four types of compositions in fluorinated SEI that work synergistically to enhance SEI performance.For instance,combining compounds with LiF can further enhance the mechanical strength and ionic conductivity of the SEI.Integrating metals with LiF significantly improves electrochemical performance at the SEI/anode interface,with a necessary focus on reducing electron tunneling risks.Additionally,incorporating polymers with LiF offers balanced improvements in interfacial toughness and ionic conductivity,though maintaining structural stability over long cycles remains a critical area for future research.Although alloys combined with LiF increase surface energy and lithium affinity,challenges such as dendrite growth and volume expansion persist.In summary,this paper emphasizes the crucial role of interfacial structures in LMBs and offers comprehensive guidance for future design and development efforts in battery technology.展开更多
FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium stor...FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium storage.Rational structural design is one way to overcome these drawbacks.In this work,MIL-88B-Fe-derived FeS_(2)nanoparticles/N-doped carbon nanofibers(M-FeS_(2)@CNFs)with expansion buffer capability are designed and synthesized for high-performance PIB anodes via electrospinning and subsequent sulfurization.The uniformly distributed cavity-type porous structure effectively mitigates the severe aggregation problem of FeS_(2)nanoparticles during cycling and buffers the volume change,further enhancing the potassium storage capacity.Meanwhile,the robust KF-rich solid electrolyte interphase induced by methyl trifluoroethylene carbonate(FEMC)additive improves the cycling stability of the M-FeS_(2)@CNF anode.In the electrolyte with 3 wt%FEMC,the M-FeS_(2)@CNF anode shows a reversible specific capacity of 592.7 mA h g^(-1)at 0.1 A g^(-1),an excellent rate capability of 327.1 mA h g^(-1)at 5 A g^(-1),and a retention rate 80.7%over 1000 cycles at 1 A g^(-1).More importantly,when assembled with a K_(1.84)Ni[Fe(CN)_(6)]_(0.88)·0.49H_(2)O cathode,the full battery manifests excellent cycle stability and high rate performance.This study demonstrates the significant importance of the synergistic effect of structural regulation and electrolyte optimization in achieving high cycling stability of PIBs.展开更多
The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated...The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.展开更多
The replacement of non-aqueous organic electrolytes with solid-state electrolytes(SSEs)in solid-state lithium metal batteries(SLMBs)is considered a promising strategy to address the constraints of lithium-ion batterie...The replacement of non-aqueous organic electrolytes with solid-state electrolytes(SSEs)in solid-state lithium metal batteries(SLMBs)is considered a promising strategy to address the constraints of lithium-ion batteries,especially in terms of energy density and reliability.Nevertheless,few SLMBs can deliver the required cycling performance and long-term stability for practical use,primarily due to suboptimal interface properties.Given the diverse solidification pathways leading to different interface characteristics,it is crucial to pinpoint the source of interface deterioration and develop appropriate remedies.This review focuses on Li|SSE interface issues between lithium metal anode and SSE,discussing recent advancements in the understanding of(electro)chemistry,the impact of defects,and interface evolutions that vary among different SSE species.The state-ofthe-art strategies concerning modified SEI,artificial interlayer,surface architecture,and composite structure are summarized and delved into the internal relationships between interface characteristics and performance enhancements.The current challenges and opportunities in characterizing and modifying the Li|SSE interface are suggested as potential directions for achieving practical SLMBs.展开更多
Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic react...Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic reactions in zinc perchlorate electrolytes,which is caused by the fast corrosive kinetics at room temperature.Herein,a concentrated perchlorate-based electrolyte consisting of 4.0 M Zn(ClO_(4))_(2)and saturated NaClO_(4)solution is developed to achieve dendrite-free and stable AZIBs at room temperature.The ClO_(4)−participates in the primary solvation sheath of Zn^(2+),facilitating the in situ formation of Zn_(5)(OH)_(8)Cl_(2)·H_(2)O-rich solid electrolyte interphase(SEI)to suppress the corrosion effect of ClO_(4)^(−).The Zn anode protected by the SEI achieves stable Zn plating/stripping over 3000 h.Furthermore,the MnO_(2)||Zn full cells manifest a stable specific capacity of 200 mAh·g^(−1)at 28℃and 101 mAh·g^(−1)at−20℃.This work introduces a promising approach for boosting the room-temperature performance of perchlorate-based electrolytes for AZIBs.展开更多
The addition of complexing agents to the electrolyte has been shown to be an effective method to enhance the discharge performance of magnesium-air batteries.In this work,four complexing agents:citric acid(CIT),salicy...The addition of complexing agents to the electrolyte has been shown to be an effective method to enhance the discharge performance of magnesium-air batteries.In this work,four complexing agents:citric acid(CIT),salicylic acid(SAL),2,6-dihydroxybenzoic acid(2,6-DHB),and 5-sulfoisophthalic acid(5-sulfoSAL)were selected as potential candidates.Through electrochemical tests,full-cell discharge experiments,and physicochemical characterization,the impact of these complexing agents on the discharge performance of magnesium-air batteries using AZ31 alloy as the anode material was investigated.The results demonstrated that the four complexing agents increased the discharge voltage of the batteries.Notably,SAL could significantly improve the anodic efficiency and the discharge specific capacity,achieving an anodic efficiency of 60.3%and a specific capacity of 1358.3 mA·h/g at a discharge current density of 10 mA/cm^(2).展开更多
Unstable Zn interface caused by rampant dendrite growth and parasitic side reactions always hinders the practical application of aqueous zinc metal batteries(AZMBs),Herein,tyrosine(Tyr)with high molecular polarity was...Unstable Zn interface caused by rampant dendrite growth and parasitic side reactions always hinders the practical application of aqueous zinc metal batteries(AZMBs),Herein,tyrosine(Tyr)with high molecular polarity was introduced into aqueous electrolyte to modulate the interfacial electrochemistry of Zn anode.In AZMBs,the positively charged side of Tyr can be well adsorbed on the surface of Zn anode to form a water-poor layer,and the exposed carboxylate side can be easily coordinated with Zn^(2+),favoring inducing uniform plating of Zn^(2+)and inhibiting the occurrence of water-induced side reactions.These in turn enable the achievement of highly stable Zn anode.Accordingly,the Zn anodes achieve outstanding cyclic stability(3000 h at 2 mA cm^(-2),2 mA h cm^(-2)and 1300 h at 5 mA cm^(-2),5 mA h cm^(-2)),high average Coulombic efficiency(99.4%over 3200 cycles),and high depth of discharge(80%for 500 h).Besides,the assembled Zn‖NaV_(3)O_(8)·1.5H_(2)O full cells deliver remarkable capacity retention and ultra-long lifetime(61.8%over 6650 cycles at 5 A g^(-1))and enhanced rate capability(169 mA h g^(-1)at 5 A g^(-1)).The work may promote the design and deep understanding of electrolyte additives with high molecular polarity for high-performance AZMBs.展开更多
Zinc-ion hybrid supercapacitors(ZHSs)are promising energy storage systems integrating high energy density and high-power density,whereas they are plagued by the poor electrochemical stability and inferior kinetics of ...Zinc-ion hybrid supercapacitors(ZHSs)are promising energy storage systems integrating high energy density and high-power density,whereas they are plagued by the poor electrochemical stability and inferior kinetics of zinc anodes.Herein,we report an electrolyte additive-assembled interconnecting molecules-zinc anode interface,realizing highly stable and fast-kinetics zinc anodes for ZHSs.The sulfobutyl groups-graftedβ-cyclodextrin(SC)supramolecules as a trace additive in ZnSO_(4)electrolytes not only adsorb on zinc anodes but also self-assemble into an interconnecting molecule interface benefiting from the mutual attraction between the electron-rich sulfobutyl group and the electron-poor cavity of the adjacent SC supramolecule.The interconnecting molecules-zinc anode interface provides abundant anion-trapping cavities and zincophilic groups to enhance Zn^(2+)transference number and homogenize Zn^(2+)deposition sites,and meanwhile,it accelerates the desolvation of hydrated Zn^(2+)to improve zinc deposition kinetics and inhibit active water molecules from inducing parasitic reactions at the zinc deposition interface,making zinc anodes present superior reversibility with 99.7%Coulombic efficiency,~30 times increase in operation lifetime and an outstanding cumulative capacity at large current densities.ZHSs with 20,000-cycle life and optimized rate capability are thereby achieved.This work provides an inspiring strategy for designing zinc anode interfaces to promote the development of ZHSs.展开更多
Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by s...Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by side reactions and dendritic growth always severely worsens the long-term operation of AZIBs.Herein,a novel 3-cyclobutene sulfone(CS)additive was employed in the aqueous electrolyte to achieve a highly reversible Zn anode.The CS additive can offer strong electronegativity and high binding energy for the coordination with Zn^(2+),which enables its entry into the solvent sheath structure of Zn^(2+)and eliminates the free H_(2)O molecules from the solvated{Zn^(2+)-SO_(4)^(2-)-(H_(2)O)_(5)}.Thus,the occurrence of side reactions and dendritic growth can be effectively inhibited.Accordingly,the Zn anode achieves long cycle-life(1400 h at 1 m A cm^(-2),1 m Ah cm^(-2),and 400 h at 5 m A cm^(-2),5 m Ah cm^(-2))and high average coulombic efficiency(99.5% over 500 cycles at 10 m A cm^(-2),1 m Ah cm^(-2)).Besides,the assembled Zn||NH_(4)V_(4)O_(10)full cell suggests enhanced cycling reversibility(123.8 m Ah g^(-1)over 500 cycles at 2 A g^(-1),84.9 m Ah g^(-1)over 800 cycles at 5 A g^(-1))and improved rate capability(139.1 m Ah g^(-1)at 5 A g^(-1)).This work may exhibit the creative design and deep understanding of sulfone-based electrolyte additives for the achievement of high-performance AZIBs.展开更多
Aqueous zinc-ion batteries(AZIBs)have developed rapidly in recent years but still face several challenges,including zinc dendrites growth,hydrogen evolution reaction,passivation and corrosion.The pH of the electrolyte...Aqueous zinc-ion batteries(AZIBs)have developed rapidly in recent years but still face several challenges,including zinc dendrites growth,hydrogen evolution reaction,passivation and corrosion.The pH of the electrolyte plays a crucial role in these processes,significantly impacting the stability and reversibility of Zn^(2+)deposition.Therefore,pH-buffer tris(hydroxymethyl)amino methane(tris)is chosen as a versatile electrolyte additive to address these issues.Tris can buffer electrolyte pH at Zn/electrolyte interface by protonated/deprotonated nature of amino group,optimize the coordination environment of zinc solvate ions by its strong interaction with zinc ions,and simultaneously create an in-situ stable solid electrolyte interface membrane on the zinc anode surface.These synergistic effects effectively restrain dendrite formation and side reactions,resulting in a highly stable and reversible Zn anode,thereby enhancing the electrochemical performance of AZIBs.The Zn||Zn battery with 0.15 wt%tris additives maintains stable cycling for 1500 h at 4 mA·cm^(−2) and 1120 h at 10 mA·cm^(−2).Furthermore,the Coulombic efficiency reaches~99.2%at 4 mA·cm^(−2)@1 mAh·cm^(−2).The Zn||NVO full batteries also demonstrated a stable specific capacity and exceptional capacity retention.展开更多
基金supported by the National Key R&D Program of China(No.2023YFB3809500)the National Natural Science Foundation of China(No.U23A20555,52202211)+3 种基金the Ninth Young Elite Scientists Sponsorship Program by CAST(2023QNRC001)the Chongqing Technology Innovation and Application Development Project(No.CSTB2022TIAD-KPX0028)the Fundamental Research Funds for the Central Universities(2023CDJXY-018)the Venture&Innovation Support Program for Chongqing Overseas Returnees(cx2022119,cx2023087).
文摘Rechargeable magnesium batteries(RMBs),as a low-cost,high-safety and high-energy storage technology,have attracted tremendous attention in large-scale energy storage applications.However,the key anode/electrolyte interfacial issues,including surface passivation,uneven Mg plating/stripping,and pulverization after cycling still result in a large overpotential,short cycling life,poor power density,and possible safety hazards of cells,severely impeding the commercial development of RMBs.In this review,a concise overview of recently advanced strategies to address these anode/electroyte interfacial issues is systematically classified and summarized.The design of magnesiophilic substrates,construction of artificial SEI layers,and modification of electrolyte are important and effective strategies to improve the uniformity/kinetics of Mg plating/stripping and achieve the stable anode/electrolyte interface.The key opportunities and challenges in this field are advisedly put forward,and the insights into future directions for stabilizing Mg metal anodes and the anode/electrolyte interface are highlighted.This review provides important references fordeveloping the high-performance and high-safety RMBs.
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 Natural Science Foundation of China(Nos.52125202,52202100,and U24A2065)the Natural Science Foundation of Jiangsu Province(BK20243016)Fundamental Research Funds for the Central Universities,China Postdoctoral Science Foundation(No.2024T171166).
文摘Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.
基金support from the Heilongjiang Province"Double First Class"Discipline Collaborative Innovation Project(No.LJGXCG2023-061).
文摘Hard carbon is a vital anode material for sodium-ion batteries;however,the nonuniform growth of solid electrolyte interphase(SEI)film substantially diminishes its initial coulombic efficiency(ICE)and cycle life.The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions.In this study,we have tuned orbital hybridization states forming an interface enriched with sp^(2) hybridized carbon(sp^(2)-C),which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation.Benefiting from successfully constructed inorganic-rich SEI,the ICE increased to 91%and sodium storage capacity reached 346 mAh/g.Besides,the capacity retention rate was 90.7%after 700 cycles at 1 A/g higher than pristine electrode(83.8%).
基金supported by a Discovery Early Career Researcher Award (DECRA,No.DE180101478) of the Australian Research CouncilNational Natural Science Foundation of China (Youth Program,No.52204378).
文摘Aqueous-electrolyte-based zinc-ion batteries(ZIBs),which have significant advantages over other batteries,including low cost,high safety,high ionic conductivity,and a natural abundance of zinc,have been regarded as a potential alternative to lithium-ion batteries(LIBs).ZIBs still face some critical challenges,however,especially for building a reversible zinc anode.To address the reversibility of zinc anode,great efforts have been made on intrinsic anode engineering and anode interface modification.Less attention has been devoted to the electrolyte additives,however,which could not only significantly improve the reversibility of zinc anode,but also determine the viability and overall performance of ZIBs.This review aims to provide an overview of the two main functions of electrolyte additives,followed by details on six reasons why additives might improve the performance of ZIBs from the perspectives of creating new layers and regulating current plating/stripping processes.Furthermore,the remaining difficulties and potential directions for additives in aqueous ZIBs are also highlighted.
基金the Doctoral Research Start-up Fund of Hubei University of Science and Technology(BK202504)the Natural Science Foundation of Liaoning Province(2023-MS-115)。
文摘The practical application of aqueous zinc-ion batteries(AZIBs)is primarily constrained by issues such as corrosion,zinc dendrite formation,and the hydrogen evolution reaction occurring at the zinc metal anode.To overcome these challenges,strategies for optimizing the electrolyte are crucial for enhancing the stability of the zinc anode.Inspired by the role of hemoglobin in blood cells,which facilitates oxygen transport during human respiration,an innovative inorganic colloidal electrolyte has been developed:calcium silicate-ZnSO_(4)(denoted as CS-ZSO).This electrolyte operates in weak acidic environment and releases calcium ions,which participate in homotopic substitution with zinc ions,while the solvation environment of hydrated zinc ions in the electrolyte is regulated.The reduced energy barrier for the transfer of zinc ions and the energy barrier for the desolvation of hydrated ions imply faster ion transfer kinetics and accelerated desolvation processes,thus favoring the mass transfer process.Furthermore,the silicate colloidal particles act as lubricants,improving the transfer of zinc ions.Together,these factors contribute to the more uniform concentration of zinc ions at the electrode/electrolyte interface,effectively inhibiting zinc dendrite formation and reducing by-product accumulation.The Zn//CS-ZSO//Zn symmetric cell demonstrates stable operation for over 5000 h at 1 mA cm^(-2),representing 29-fold improvement compared to the Zn//ZSO//Zn symmetric cell,which lasts only 170 h.Additionally,the Zn//CS-ZSO//Cu asymmetric cell shows stable average Coulombic efficiency(CE)exceeding 99.6%over2400 cycles,significantly surpassing the performance of the ZSO electrolyte.This modification strategy for electrolytes not only addresses key limitations associated with zinc anodes but also provides valuable insights into stabilizing anodes for the advancement of high-performance aqueous zinc-ion energy storage systems.
基金National Natural Science Foundation of China (52073253)。
文摘Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of sodium-potassium(NaK)alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the physical contact of the electrode-electrolyte interface.Additionally,the filling of SiO_(2) nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 hrs.The full cell coupled with Na_(3)V_(2)(PO_(4))_(2) cathodes had an initial discharge capacity of 106.8 mAh·g^(-1) with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1) even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.
基金supported by National Natural Science Foundation of China(No.22205182)National Science Fund for Distinguished Young Scholars(No.52025034)+2 种基金China Postdoctoral Science Foundation(Nos.2022M722594/2024T171170)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515011516)financially supported by Innovation Team of Shaanxi Sanqin Scholars。
文摘The development of lithium-ion batteries with high-energy densities is substantially hampered by the graphite anode's low theoretical capacity(372 mAh g^(-1)).There is an urgent need to explore novel anode materials for lithium-ion batteries.Silicon(Si),the second-largest element outside of Earth,has an exceptionally high specific capacity(3579 mAh g^(-1)),regarded as an excellent choice for the anode material in high-capacity lithium-ion batteries.However,it is low intrinsic conductivity and volume amplification during service status,prevented it from developing further.These difficulties can be successfully overcome by incorporating carbon into pure Si systems to form a composite anode and constructing a buffer structure.This review looks at the diffusion mechanism,various silicon-based anode material configurations(including sandwich,core-shell,yolk-shell,and other 3D mesh/porous structures),as well as the appropriate binders and electrolytes.Finally,a summary and viewpoints are offered on the characteristics and structural layout of various structures,metal/non-metal doping,and the compatibility and application of various binders and electrolytes for silicon-based anodes.This review aims to provide valuable insights into the research and development of silicon-based carbon anodes for high-performance lithium-ion batteries,as well as their integration with binders and electrolyte.
基金supported by the National Natural Science Foundation of China(51763014 and 52073133)Key Talent Project Foundation of Gansu Province+1 种基金Joint fund between Shenyang National Laboratory for Materials Science and State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals(18LHPY002)the Program for Hong Liu Distinguished Young Scholars in Lanzhou University of Technology。
文摘Aqueous zinc metal batteries have garnered substantial attention ascribing to affordability,intrinsic safety,and environmental benignity Nevertheless,zinc metal batteries yet are challenged with potential service life issues resulted from dendrites and side reaction.In this paper,a strategy of nanoparticles doped hydrogel is proposed for constructing carboxymethyl cellulose/graphite oxide hybrid hydrogel electrolyte membranes with exceptional ionic conductivity,anti-swelling property,and simultaneously addressing the dendrites and parasitic reaction.The pivotal functions of the carboxymethyl cellulose/graphite oxide hydrogel electrolyte in mitigating hydrogen evolution and fostering accelerated Zn deposition have been elucidated based on principles of thermodynamic and reaction kinetic.The carboxymethyl cellulose/graphite oxide hydrogel electrolyte endows exceptional cycling longevity(800 h at 1 mA cm^(-2)/1 mAh cm^(-2))for Znjj Zn battery,as well as high Coulombic efficiency for Znjj Cu battery(averagely 99.14%within 439 cycles at 1 mA cm^(-2)/1 mAh cm^(-2)).The assembled Znjj NH_(4)V_(4)O_(10)battery delivers a high reversible specific capacity of 328.5 mAh g^(-1)at 0.1 A g^(-1).Moreover,the device of Znjj NH_(4)V_(4)O_(10)pouch battery remains operational under severe conditions like bending and cutting.This work provides valuable reference in developing inorganic nanoparticle hybrid hydrogel electrolyte for realizing high-performance zinc metal batteries.
基金financially supported by the Energy Revolution S&T Program of Yulin Innovation Institute of Clean Energy(E411060316)the NSFC-CONICFT Joint Project(51961125207)+1 种基金the Special Fund(2024)of Basic Scientific Research Project at Undergraduate University in Liaoning Province(LJ212410152056)the Foundation(GZKF202301)of State Key Laboratory of Biobased Material and Green Papermaking,Qilu University of Technology,Shandong Academy of Sciences。
文摘Aqueous zinc-iodine(Zn-I_(2))batteries show great potential as energy storage candidates due to their high-safety and low-cost,but confronts hydrogen evolution reaction(HER)and dendrite growth at anode side and polyiodide shuttling at cathode side.Herein,"tennis racket"(TR)hydrogel electrolytes were prepared by the co-polymerization and co-blending of polyacrylamide(PAM),sodium lignosulfonate(SL),and sodium alginate(SA)to synchronously regulate cathode and anode of Zn-I_(2)batteries."Gridline structure"of TR can induce the uniform transportation of Zn^(2+)ions through the coordination effect to hinder HER and dendrite growth at anode side,as well as hit I_(3)^(-)ions as"tennis"via the strong repulsion force to avoid shuttle effect at cathode side.The synergistic effect of TR electrolyte endows Zn-Zn symmetric battery with high cycling stability over 4500 h and Zn-I_(2)cell with the stably cycling life of 15000 cycles at5 A g^(-1),outperforming the reported works.The practicability of TR electrolyte is verified by flexible Zn-I_(2)pouch battery.This work opens a route to synchronously regulate cathode and anode to enhance the electrochemical performance of Zn-I_(2)batteries.
基金support from the National Natural Science Foundation of China(No.U2333210)the Sichuan Science and Technology Program,China(No.21SYSX0011)。
文摘Lithium metal batteries(LMBs)are emerging as a promising energy storage solution owing to their high energy density and specific capacity.However,the non-uniform plating of lithium and the potential rupture of the solid-electrolyte interphase(SEI)during extended cycling use may result in dendrite growth,which can penetrate the separator and pose significant short-circuit risks.Forming a stable SEI is essential for the long-term operation of the batteries.Fluorine-rich SEI has garnered significant attention for its ability to effectively passivate electrodes,regulate lithium deposition,and inhibit electrolyte corrosion.Understanding the structural components and preparation methods of existing fluorinated SEI is crucial for optimizing lithium metal anode performance.This paper reviews the research on optimizing LiF passivation interfaces to protect lithium metal anodes.It focuses on four types of compositions in fluorinated SEI that work synergistically to enhance SEI performance.For instance,combining compounds with LiF can further enhance the mechanical strength and ionic conductivity of the SEI.Integrating metals with LiF significantly improves electrochemical performance at the SEI/anode interface,with a necessary focus on reducing electron tunneling risks.Additionally,incorporating polymers with LiF offers balanced improvements in interfacial toughness and ionic conductivity,though maintaining structural stability over long cycles remains a critical area for future research.Although alloys combined with LiF increase surface energy and lithium affinity,challenges such as dendrite growth and volume expansion persist.In summary,this paper emphasizes the crucial role of interfacial structures in LMBs and offers comprehensive guidance for future design and development efforts in battery technology.
基金supported by the National Natural Science Foundation of China(22179063,22479078,and 22409093)the Natural Science Foundation of Jiangsu Province of China(BK20240579)。
文摘FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium storage.Rational structural design is one way to overcome these drawbacks.In this work,MIL-88B-Fe-derived FeS_(2)nanoparticles/N-doped carbon nanofibers(M-FeS_(2)@CNFs)with expansion buffer capability are designed and synthesized for high-performance PIB anodes via electrospinning and subsequent sulfurization.The uniformly distributed cavity-type porous structure effectively mitigates the severe aggregation problem of FeS_(2)nanoparticles during cycling and buffers the volume change,further enhancing the potassium storage capacity.Meanwhile,the robust KF-rich solid electrolyte interphase induced by methyl trifluoroethylene carbonate(FEMC)additive improves the cycling stability of the M-FeS_(2)@CNF anode.In the electrolyte with 3 wt%FEMC,the M-FeS_(2)@CNF anode shows a reversible specific capacity of 592.7 mA h g^(-1)at 0.1 A g^(-1),an excellent rate capability of 327.1 mA h g^(-1)at 5 A g^(-1),and a retention rate 80.7%over 1000 cycles at 1 A g^(-1).More importantly,when assembled with a K_(1.84)Ni[Fe(CN)_(6)]_(0.88)·0.49H_(2)O cathode,the full battery manifests excellent cycle stability and high rate performance.This study demonstrates the significant importance of the synergistic effect of structural regulation and electrolyte optimization in achieving high cycling stability of PIBs.
基金financially supported by Jilin Province Science and Technology Department Program(Nos.YDZJ202201ZYTS304,20220201130GX and 20240101004JJ)the National Natural Science Foundation of China(Nos.52171210 and 52471229)the Science and Technology Project of Jilin Provincial Education Department(No.JJKH20220428KJ)
文摘The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.
基金Financial support from National Key R&D Program(2022YFB2404600)Natural Science Foundation of China(Key Project of 52131306)+1 种基金Project on Carbon Emission Peak and Neutrality of Jiangsu Province(BE2022031-4)the Big Data Computing Center of Southeast University are greatly appreciated.
文摘The replacement of non-aqueous organic electrolytes with solid-state electrolytes(SSEs)in solid-state lithium metal batteries(SLMBs)is considered a promising strategy to address the constraints of lithium-ion batteries,especially in terms of energy density and reliability.Nevertheless,few SLMBs can deliver the required cycling performance and long-term stability for practical use,primarily due to suboptimal interface properties.Given the diverse solidification pathways leading to different interface characteristics,it is crucial to pinpoint the source of interface deterioration and develop appropriate remedies.This review focuses on Li|SSE interface issues between lithium metal anode and SSE,discussing recent advancements in the understanding of(electro)chemistry,the impact of defects,and interface evolutions that vary among different SSE species.The state-ofthe-art strategies concerning modified SEI,artificial interlayer,surface architecture,and composite structure are summarized and delved into the internal relationships between interface characteristics and performance enhancements.The current challenges and opportunities in characterizing and modifying the Li|SSE interface are suggested as potential directions for achieving practical SLMBs.
基金supported by Hainan Provincial Joint Project of Sanya Yazhou Bay Science and Technology City(No.2021JJLH0069)the Project of Sanya Yazhou Bay Science and Technology City(No.SCKJ-JYRC-2023-55)Hainan Provincial Natural Science Foundation of China(No.522CXTD516).
文摘Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic reactions in zinc perchlorate electrolytes,which is caused by the fast corrosive kinetics at room temperature.Herein,a concentrated perchlorate-based electrolyte consisting of 4.0 M Zn(ClO_(4))_(2)and saturated NaClO_(4)solution is developed to achieve dendrite-free and stable AZIBs at room temperature.The ClO_(4)−participates in the primary solvation sheath of Zn^(2+),facilitating the in situ formation of Zn_(5)(OH)_(8)Cl_(2)·H_(2)O-rich solid electrolyte interphase(SEI)to suppress the corrosion effect of ClO_(4)^(−).The Zn anode protected by the SEI achieves stable Zn plating/stripping over 3000 h.Furthermore,the MnO_(2)||Zn full cells manifest a stable specific capacity of 200 mAh·g^(−1)at 28℃and 101 mAh·g^(−1)at−20℃.This work introduces a promising approach for boosting the room-temperature performance of perchlorate-based electrolytes for AZIBs.
基金supported by the National Natural Science Foundation of China(No.52001015)the Urban Carbon Neutral Science Innovation Foundation of Beijing University of Technology,China(No.053000514124601)the Science and Technology Program of Beijing Municipal Education Commission,China(No.KM201810005007).
文摘The addition of complexing agents to the electrolyte has been shown to be an effective method to enhance the discharge performance of magnesium-air batteries.In this work,four complexing agents:citric acid(CIT),salicylic acid(SAL),2,6-dihydroxybenzoic acid(2,6-DHB),and 5-sulfoisophthalic acid(5-sulfoSAL)were selected as potential candidates.Through electrochemical tests,full-cell discharge experiments,and physicochemical characterization,the impact of these complexing agents on the discharge performance of magnesium-air batteries using AZ31 alloy as the anode material was investigated.The results demonstrated that the four complexing agents increased the discharge voltage of the batteries.Notably,SAL could significantly improve the anodic efficiency and the discharge specific capacity,achieving an anodic efficiency of 60.3%and a specific capacity of 1358.3 mA·h/g at a discharge current density of 10 mA/cm^(2).
基金the financial support from the Foshan Talents Special Foundation(BKBS202003).
文摘Unstable Zn interface caused by rampant dendrite growth and parasitic side reactions always hinders the practical application of aqueous zinc metal batteries(AZMBs),Herein,tyrosine(Tyr)with high molecular polarity was introduced into aqueous electrolyte to modulate the interfacial electrochemistry of Zn anode.In AZMBs,the positively charged side of Tyr can be well adsorbed on the surface of Zn anode to form a water-poor layer,and the exposed carboxylate side can be easily coordinated with Zn^(2+),favoring inducing uniform plating of Zn^(2+)and inhibiting the occurrence of water-induced side reactions.These in turn enable the achievement of highly stable Zn anode.Accordingly,the Zn anodes achieve outstanding cyclic stability(3000 h at 2 mA cm^(-2),2 mA h cm^(-2)and 1300 h at 5 mA cm^(-2),5 mA h cm^(-2)),high average Coulombic efficiency(99.4%over 3200 cycles),and high depth of discharge(80%for 500 h).Besides,the assembled Zn‖NaV_(3)O_(8)·1.5H_(2)O full cells deliver remarkable capacity retention and ultra-long lifetime(61.8%over 6650 cycles at 5 A g^(-1))and enhanced rate capability(169 mA h g^(-1)at 5 A g^(-1)).The work may promote the design and deep understanding of electrolyte additives with high molecular polarity for high-performance AZMBs.
基金the National Key R&D Program of China(2022YFB2404500)Guangdong Basic and Applied Basic Research Foundation(2023A1515110347+2 种基金2023A1515012087)Funding by Science and Technology Projects in Guangzhou(2024A04J3267)the Fundamental Research Funds for the Central Universities(21624411).
文摘Zinc-ion hybrid supercapacitors(ZHSs)are promising energy storage systems integrating high energy density and high-power density,whereas they are plagued by the poor electrochemical stability and inferior kinetics of zinc anodes.Herein,we report an electrolyte additive-assembled interconnecting molecules-zinc anode interface,realizing highly stable and fast-kinetics zinc anodes for ZHSs.The sulfobutyl groups-graftedβ-cyclodextrin(SC)supramolecules as a trace additive in ZnSO_(4)electrolytes not only adsorb on zinc anodes but also self-assemble into an interconnecting molecule interface benefiting from the mutual attraction between the electron-rich sulfobutyl group and the electron-poor cavity of the adjacent SC supramolecule.The interconnecting molecules-zinc anode interface provides abundant anion-trapping cavities and zincophilic groups to enhance Zn^(2+)transference number and homogenize Zn^(2+)deposition sites,and meanwhile,it accelerates the desolvation of hydrated Zn^(2+)to improve zinc deposition kinetics and inhibit active water molecules from inducing parasitic reactions at the zinc deposition interface,making zinc anodes present superior reversibility with 99.7%Coulombic efficiency,~30 times increase in operation lifetime and an outstanding cumulative capacity at large current densities.ZHSs with 20,000-cycle life and optimized rate capability are thereby achieved.This work provides an inspiring strategy for designing zinc anode interfaces to promote the development of ZHSs.
基金the financial support from the Foshan Talents Special Foundation(BKBS202003)。
文摘Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by side reactions and dendritic growth always severely worsens the long-term operation of AZIBs.Herein,a novel 3-cyclobutene sulfone(CS)additive was employed in the aqueous electrolyte to achieve a highly reversible Zn anode.The CS additive can offer strong electronegativity and high binding energy for the coordination with Zn^(2+),which enables its entry into the solvent sheath structure of Zn^(2+)and eliminates the free H_(2)O molecules from the solvated{Zn^(2+)-SO_(4)^(2-)-(H_(2)O)_(5)}.Thus,the occurrence of side reactions and dendritic growth can be effectively inhibited.Accordingly,the Zn anode achieves long cycle-life(1400 h at 1 m A cm^(-2),1 m Ah cm^(-2),and 400 h at 5 m A cm^(-2),5 m Ah cm^(-2))and high average coulombic efficiency(99.5% over 500 cycles at 10 m A cm^(-2),1 m Ah cm^(-2)).Besides,the assembled Zn||NH_(4)V_(4)O_(10)full cell suggests enhanced cycling reversibility(123.8 m Ah g^(-1)over 500 cycles at 2 A g^(-1),84.9 m Ah g^(-1)over 800 cycles at 5 A g^(-1))and improved rate capability(139.1 m Ah g^(-1)at 5 A g^(-1)).This work may exhibit the creative design and deep understanding of sulfone-based electrolyte additives for the achievement of high-performance AZIBs.
基金supported by the Fund of Xuzhou Science and Technology Key R&D Program(Social Development)Project(No.KC22289)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX22_2783).
文摘Aqueous zinc-ion batteries(AZIBs)have developed rapidly in recent years but still face several challenges,including zinc dendrites growth,hydrogen evolution reaction,passivation and corrosion.The pH of the electrolyte plays a crucial role in these processes,significantly impacting the stability and reversibility of Zn^(2+)deposition.Therefore,pH-buffer tris(hydroxymethyl)amino methane(tris)is chosen as a versatile electrolyte additive to address these issues.Tris can buffer electrolyte pH at Zn/electrolyte interface by protonated/deprotonated nature of amino group,optimize the coordination environment of zinc solvate ions by its strong interaction with zinc ions,and simultaneously create an in-situ stable solid electrolyte interface membrane on the zinc anode surface.These synergistic effects effectively restrain dendrite formation and side reactions,resulting in a highly stable and reversible Zn anode,thereby enhancing the electrochemical performance of AZIBs.The Zn||Zn battery with 0.15 wt%tris additives maintains stable cycling for 1500 h at 4 mA·cm^(−2) and 1120 h at 10 mA·cm^(−2).Furthermore,the Coulombic efficiency reaches~99.2%at 4 mA·cm^(−2)@1 mAh·cm^(−2).The Zn||NVO full batteries also demonstrated a stable specific capacity and exceptional capacity retention.
