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
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
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-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
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
H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an elec...H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an electrolyte additive to solve the above issues by three aspects:Firstly,Met is anchored on Zn anode by amino/methylthio groups to form a H_(2)O-poor AEI,thus increasing the overpotential of hydrogen evolution reaction(HER);secondly,Met serves as a pH buffer to neutralize the HER generated OH-,thereby preventing the formation of by-products(e.g.Zn_(4)SO_(4)(OH)_(6)·xH_(2)O);thirdly,Zn^(2+) could be captured by carboxyl group of the anchored Met through electrostatic interaction,which promotes the dense and flat Zn deposition.Consequently,the Zn||Zn symmetric cell obtains a long cycle life of 3200 h at 1.0 mA cm^(-2),1.0 mAh cm^(-2),and 1400 h at 5.0 mA cm^(-2),5.0 mAh cm^(-2).Moreover,Zn||VO_(2) full cell exhibits a capacity retention of 91.0%after operating for 7000 cycles at 5.0 A g^(-1).This study offers a novel strategy for modulating the interface microenvironment of AEI via integrating the molecular adsorption,pH buffer,and Zn^(2+) capture strategies to design advanced industrial-oriented batteries.展开更多
Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,saf...Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries.Current research efforts primarily focus on altering the solvated structure of Li+by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier,expedite the desolvation process,and suppress the growth of lithium dendrites.Nevertheless,an integrated approach that combines the advantages of these two strategies remains elusive.In this study,we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process,reduce the nucleation barrier of Li+,and modulate its solvated structure.This approach enhanced the inorganic compound content in the solid electrolyte interphase(SEI)on lithium foil surfaces,leading to stable Li+deposition and stripping.Specifically,Li||Cu cells demonstrated excellent cycle life and Coulombic efficiency(97.28%and 98.59%,respectively)at 0.5 m A/cm^(2)@0.5 m Ah/cm^(2)and 1 m A/cm^(2)@1 m Ah/cm^(2)for 410 and 240 cycles,respectively.Li||Li symmetrical cells showed no short circuit at 1 m A/cm^(2)@1 m Ah/cm^(2)for 1150 h,and Li||LFP full cells retained 68.9%of their capacity(104.6 m Ah/g)after 250 cycles at N/P(1.1:1.0)with a current density of 1C.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
The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research.However,the practical implementation of lithium metal anodes is impeded b...The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research.However,the practical implementation of lithium metal anodes is impeded by challenges such as dendrite formation and the inherent instability of the native oxide layer.This study introduces a novel liquid-source plasma technique to create a high-quality solid electrolyte interphase(SEI)composed of LiBr and LiBO_(2).According to first-principal calculation,LiBO_(2)optimizes the electrochemical dynamics and LiBr improves Li diffusion at the interfaces,thus protecting the Li metal from severe Li dendrite growth.This well-designed artificial SEI endows the Li metal with remarkable cycling stability over 550 cycles at a current density of 1 m A/cm^(2),significantly superior to the bare Li anode.Meanwhile,the full cell paired with a high-voltage LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)cathode delivers long-term stability with capacity retention(78%after 200 cycles)at 1 C and excellent rate performance.The findings highlight the importance of interface engineering in optimizing battery performance and longevity.展开更多
Silicon suboxide(SiO_(x),0<x<2)is an appealing anode material to replace traditional graphite owing to its much higher theoretical specific capacity enabling higher-energy-density lithium batteries.Nevertheless,...Silicon suboxide(SiO_(x),0<x<2)is an appealing anode material to replace traditional graphite owing to its much higher theoretical specific capacity enabling higher-energy-density lithium batteries.Nevertheless,the huge volume change and rapid capacity decay of SiO_(x)electrodes during cycling pose huge challenges to their large-scale practical applications.To eliminate this bottleneck,a dragonfly wing microstructure-inspired polymer electrolyte(denoted as PPM-PE)is developed based on in-situ polymerization of bicyclic phosphate ester-and urethane motif-containing monomer and methyl methacrylate in traditional liquid electrolyte.PPM-PE delivers excellent mechanical properties,highly correlated with the formation of a micro-phase separation structure similar with dragonfly wings.By virtue of superior mechanical properties and the in-situ solidified preparation method,PPM-PE can form a 3D polymer network buffer against stress within the electrode particles gap,enabling much suppressed electrode volume expansion and more stabilized solid electrolyte interface along with evidently decreased electrolyte decomposition.Resultantly,PPM-PE shows significant improvements in both cycling and rate performance in button and soft package batteries with SiO_(x)-based electrodes,compared with the liquid electrolyte counterpart.Such a dragonfly wing microstructure-inspired design philosophy of in-situ solidified polymer electrolytes helps facilitate the practical implementation of high-energy lithium batteries with SiO_(x)-based anodes.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supported by a Discovery Early Career Researcher Award(DECRA,No.DE180101478)of the Australian Research Council and National 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 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.
基金supported by the National Natural Science Foundation of China(22479031,22162004)the Natural Science Foundation of Guangxi(2022JJD120011).
文摘H_(2)O-induced side reactions and dendrite growth occurring at the Zn anode-electrolyte interface(AEI)limit the electrochemical performances of aqueous zinc ion batteries.Herein,methionine(Met)is introduced as an electrolyte additive to solve the above issues by three aspects:Firstly,Met is anchored on Zn anode by amino/methylthio groups to form a H_(2)O-poor AEI,thus increasing the overpotential of hydrogen evolution reaction(HER);secondly,Met serves as a pH buffer to neutralize the HER generated OH-,thereby preventing the formation of by-products(e.g.Zn_(4)SO_(4)(OH)_(6)·xH_(2)O);thirdly,Zn^(2+) could be captured by carboxyl group of the anchored Met through electrostatic interaction,which promotes the dense and flat Zn deposition.Consequently,the Zn||Zn symmetric cell obtains a long cycle life of 3200 h at 1.0 mA cm^(-2),1.0 mAh cm^(-2),and 1400 h at 5.0 mA cm^(-2),5.0 mAh cm^(-2).Moreover,Zn||VO_(2) full cell exhibits a capacity retention of 91.0%after operating for 7000 cycles at 5.0 A g^(-1).This study offers a novel strategy for modulating the interface microenvironment of AEI via integrating the molecular adsorption,pH buffer,and Zn^(2+) capture strategies to design advanced industrial-oriented batteries.
基金supported by Yunnan Natural Science Foundation Project(No.202202AG050003)Yunnan Fundamental Research Projects(Nos.202101BE070001-018 and 202201AT070070)+1 种基金the National Youth Talent Support Program of Yunnan Province China(No.YNQR-QNRC-2020-011)Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects(No.2023-XMDJ-00617107)。
文摘Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries.Current research efforts primarily focus on altering the solvated structure of Li+by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier,expedite the desolvation process,and suppress the growth of lithium dendrites.Nevertheless,an integrated approach that combines the advantages of these two strategies remains elusive.In this study,we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process,reduce the nucleation barrier of Li+,and modulate its solvated structure.This approach enhanced the inorganic compound content in the solid electrolyte interphase(SEI)on lithium foil surfaces,leading to stable Li+deposition and stripping.Specifically,Li||Cu cells demonstrated excellent cycle life and Coulombic efficiency(97.28%and 98.59%,respectively)at 0.5 m A/cm^(2)@0.5 m Ah/cm^(2)and 1 m A/cm^(2)@1 m Ah/cm^(2)for 410 and 240 cycles,respectively.Li||Li symmetrical cells showed no short circuit at 1 m A/cm^(2)@1 m Ah/cm^(2)for 1150 h,and Li||LFP full cells retained 68.9%of their capacity(104.6 m Ah/g)after 250 cycles at N/P(1.1:1.0)with a current density of 1C.
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supported by National Natural Science Foundation of China(Nos.52372235,52073252,52002052,U20A20253,21972127,22279116)Key Scientific Research Project of Hangzhou(No.2024SZD1B12)+5 种基金Science and Technology Department of Zhejiang Province(Nos.2023C01231,Q23E020046,LD22E020006LY21E020005)Key Research and Development Project of Science and Technology Department of Sichuan Province(No.2022YFSY0004)Natural Science Foundation of Zhejiang Province(No.LQ23E020009)Sichuan Natural Science(No.2024NSFSC0951)Key Laboratory of Engineering Dielectrics and Its Application(Harbin University of Science and Technology),Ministry of Education(No.KFM 202303)。
文摘The escalating demand for advanced energy storage solutions has positioned lithium metal anodes at the forefront of battery technology research.However,the practical implementation of lithium metal anodes is impeded by challenges such as dendrite formation and the inherent instability of the native oxide layer.This study introduces a novel liquid-source plasma technique to create a high-quality solid electrolyte interphase(SEI)composed of LiBr and LiBO_(2).According to first-principal calculation,LiBO_(2)optimizes the electrochemical dynamics and LiBr improves Li diffusion at the interfaces,thus protecting the Li metal from severe Li dendrite growth.This well-designed artificial SEI endows the Li metal with remarkable cycling stability over 550 cycles at a current density of 1 m A/cm^(2),significantly superior to the bare Li anode.Meanwhile,the full cell paired with a high-voltage LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)cathode delivers long-term stability with capacity retention(78%after 200 cycles)at 1 C and excellent rate performance.The findings highlight the importance of interface engineering in optimizing battery performance and longevity.
基金financially supported by the National Key R&D Program of China(2023YFC2812700)the Key Scientific and Technological Innovation Project of Shandong(2022CXGC020301)+6 种基金the National Natural Science Foundation of China(22279153,U22A2044,22479154,52303287)the Taishan Scholars of Shandong Province(No.ts201511063)the Shandong Energy Institute(Grant No.SEI I202108)the Postdoctoral Fellowship Program of CPSF(E31Z3F04)China Postdoctoral Science Foundation(2024 M753350)the Natural Science Foundation of Shandong Province(ZR2023QB208)Qingdao Natural Science Foundation(23-2-1-77-zyyd-jch)。
文摘Silicon suboxide(SiO_(x),0<x<2)is an appealing anode material to replace traditional graphite owing to its much higher theoretical specific capacity enabling higher-energy-density lithium batteries.Nevertheless,the huge volume change and rapid capacity decay of SiO_(x)electrodes during cycling pose huge challenges to their large-scale practical applications.To eliminate this bottleneck,a dragonfly wing microstructure-inspired polymer electrolyte(denoted as PPM-PE)is developed based on in-situ polymerization of bicyclic phosphate ester-and urethane motif-containing monomer and methyl methacrylate in traditional liquid electrolyte.PPM-PE delivers excellent mechanical properties,highly correlated with the formation of a micro-phase separation structure similar with dragonfly wings.By virtue of superior mechanical properties and the in-situ solidified preparation method,PPM-PE can form a 3D polymer network buffer against stress within the electrode particles gap,enabling much suppressed electrode volume expansion and more stabilized solid electrolyte interface along with evidently decreased electrolyte decomposition.Resultantly,PPM-PE shows significant improvements in both cycling and rate performance in button and soft package batteries with SiO_(x)-based electrodes,compared with the liquid electrolyte counterpart.Such a dragonfly wing microstructure-inspired design philosophy of in-situ solidified polymer electrolytes helps facilitate the practical implementation of high-energy lithium batteries with SiO_(x)-based anodes.
