Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temp...Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.展开更多
Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental ...Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.展开更多
Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy densit...Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy density and improved safety,making them promising alternatives for next-generation rechargeable batteries[1].As a crucial component of these batteries,solid-state electrolytes—divided into inorganic solid ceramic electrolytes(SCEs)and organic solid polymer electrolytes(SPEs)—are vital for lithium-ion transport and inhibiting lithium dendrite growth.Among them,SCEs exhibit high ionic conductivity,excellent mechanical properties,and outstanding electrochemical and thermal stability.Nevertheless,their brittleness,interfacial challenges with electrodes,and the requirement for high stacking pressure during battery operation significantly hinder their scalable application.In comparison,SPEs are more favourable for manufacturing due to their flexibility and good interfacial compatibility with electrodes[2].Despite these advantages,SPEs still face significant challenges in achieving practical application.Firstly,typical SPEs,such as poly(ethylene oxide)(PEO),poly(vinylidene fluoride)(PVDF),and poly(ethylene glycol)diacrylate(PEGDA),are characterized by high crystallinity,which causes polymer chains to be tightly packed and rigid.This restricts the segmental motion within the SPEs,resulting in low ionic conductivity.Secondly,compared to lithium ions,anions with large ionic radii and low charge density typically form weaker interactions with the polymer chains,which facilitates their mobility and results in a low lithium-ion transference number(tt).Thirdly,the weak interactions between polymer chains in typical SPEs lead to a low elastic modulus,which in turn compromises their poor mechanical strength.展开更多
Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.L...Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.Li^(+)/Li)constrains their use in ultrahighvoltage systems(e.g.,4.8 V).In this work,ferroelectric Ba TiO_(3)(BTO)nanoparticles with optimized thickness of~50-100 nm were successfully coated onto Li_(2.5)Y_(0.5)Zr_(0.5)Cl_(6)(LYZC@5BTO)electrolytes using a time-efficient ball-milling process.The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity,which remained at 1.06 m S cm^(-1)for LYZC@5BTO.Furthermore,this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes,suppresses parasitic interfacial reactions with single-crystal NCM811(SCNCM811),and inhibits the irreversible phase transition of SCNCM811.Consequently,the cycling stability of LYZC under high-voltage conditions(4.8 V vs.Li+/Li)is significantly improved.Specifically,ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 m Ah g^(-1)over 200 cycles at 1 C,way outperforming cell using pristine LYZC that only shows a capacity of 55.4 m Ah g^(-1).Furthermore,time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially,rising to 26% after 200 cycles in pristine LYZC.In contrast,LYZC@5BTO limited this increase to only 14%,confirming the effectiveness of BTO in stabilizing the interfacial chemistry.This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.展开更多
Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving...Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.展开更多
Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. Ho...Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fiuorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital(LUMO), which leads to significant consumption of the fiuorinated components upon cycling.Herein, attenuating reductive decomposition of fiuorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate(VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fiuoroethylene carbonate(FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fiuorinated electrolytes in high-voltage Li-metal batteries.展开更多
1.Introduction.The ever-increasing demands for high-energy-density power supply systems have driven the rapid development of conventional lithium-ion batteries,of which properties are approaching to the ceiling.In the...1.Introduction.The ever-increasing demands for high-energy-density power supply systems have driven the rapid development of conventional lithium-ion batteries,of which properties are approaching to the ceiling.In the meantime,the safety of lithium-ion batteries also grabs more attention as their wide application in consumer electronics and electric vehicles.The safety of battery system can be enhanced inherently by replacing the flammable liquid electrolytes with inorganic solid electrolytes,which makes solid-state battery one of the most promising candidates of next-generation energy storage systems[1-3].Additionally,the improvements in energy density are foreseen as solid electrolytes enable lithium metal anode[4-11]and high-voltage cathodes[12-15].展开更多
The constant increase in global energy demand and stricter environmental standards are calling for advanced energy storage technologies that can store electricity from intermittent renewable sources such as wind,solar...The constant increase in global energy demand and stricter environmental standards are calling for advanced energy storage technologies that can store electricity from intermittent renewable sources such as wind,solar,and tidal power,to allow the broader implementation of the renewables.The gridoriented sodium-ion batteries,potassium ion batteries and multivalent ion batteries are cheaper and more sustainable alternatives to Li-ion,although they are still in the early stages of development.Additional optimisation of these battery systems is required,to improve the energy and power density,and to solve the safety issues caused by dendrites growth in anodes.Electrolyte,one of the most critical components in these batteries,could significantly influence the electrochemical performances and operations of batteries.In this review,the definitions and influences of three critical components(salts,solvents,and additives)in electrolytes are discussed.The significant advantages,challenges,recent progress and future optimisation directions of various electrolytes for monovalent and multivalent ions batteries(i.e.organic,ionic liquid and aqueous liquid electrolytes,polymer and inorganic solid electrolytes)are summarised to guide the practical application for grid-oriented batteries.展开更多
Solvation structures fundamentally control the ion-transport dynamics and mechanical properties of polymer electrolytes.However,there is a lack of strategies to rationally regulate the solvation structures and fundame...Solvation structures fundamentally control the ion-transport dynamics and mechanical properties of polymer electrolytes.However,there is a lack of strategies to rationally regulate the solvation structures and fundamental understanding on how they control the electrochemical performances.Herein,by harnessing the electrostatic adsorption of one-dimensional nanofiller(i.e.,surface-charged halloysite nanotubes,d-HNTs),we successfully fabricate a high-performance polymer nanocomposite electrolyte enabled by strong surface adsorption,referred as adsorption-state polymer electrolyte(ASPE).This ASPE shows fast ion transport(0.71±0.05 mS cm^(-1)at room temperature),high mechanical strength and toughness(10.3±0.05 MPa;15.73 MJ m^(-3)),improved lithium-ion transference number,and long cycle life with lithium metal anode,in comparison with the sample without the d-HNT adsorption effect.To fundamentally understand these high performances,an anion-rich asymmetric solvent structure model is further proposed and evidenced by both experiments and simulation studies.Results show that the electrostatic adsorption among the d-HNT,ionic liquid electrolyte,and polymer chain generates a nano filler-supported fast ion-conduction pathway with asymmetric Li+-coordination microenvironment.Meanwhile,the anion-rich asymmetric solvent structure model of ASPE also generates a fast de-solvation and anion-derived stable solid-electrolyte interphase for lithium metal anode.The high performance and understanding of the mechanism for ASPE provide a promising path to develop advanced polymer electrolytes.展开更多
The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious int...The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.展开更多
With the widespread adoption of lithium-ion batteries(LIBs),safety concerns associated with flammable organic elec-trolytes have become increasingly critical.Solid-state lithium batteries(SSLBs),with enhanced safety a...With the widespread adoption of lithium-ion batteries(LIBs),safety concerns associated with flammable organic elec-trolytes have become increasingly critical.Solid-state lithium batteries(SSLBs),with enhanced safety and higher energy density potential,are regarded as a promising next-generation energy storage technology.However,the practical appli-cation of solid-state electrolytes(SSEs)remains hindered by several challenges,including low Li+ion conductivity,poor interfacial compatibility with electrodes,unfavorable mechanical properties and difficulties in scalable manufacturing.This review systematically examines recent progress in SSEs,including inorganic types(oxides,sulfides,halides),organic types(polymers,plastic crystals,poly(ionic liquids)(PILs)),and the emerging class of soft solid-state electrolytes(S3Es),especially those based on“rigid-flexible synergy”composites and“Li+-desolvation”mechanism using porous frameworks.Critical assessment reveals that single-component SSEs face inherent limitations that are difficult to be fully overcome through compositional and structural modification alone.In contrast,S3Es integrate the strength of complementary components to achieve a balanced and synergic enhancement in electrochemical properties(e.g.,ionic conductivity and stability window),mechanical integrity,and processability,showing great promise as next-generation SSEs.Furthermore,the application-ori-ented challenges and emerging trends in S3E research are outlined,aiming to provide strategic insights into future develop-ment of high-performance SSEs.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
Fluoropolymers promise all-solid-state lithium metal batteries(ASLMBs)but suffer from two critical challenges.The first is the trade-off between ionic conductivity(σ)and lithium anode reactions,closely related to hig...Fluoropolymers promise all-solid-state lithium metal batteries(ASLMBs)but suffer from two critical challenges.The first is the trade-off between ionic conductivity(σ)and lithium anode reactions,closely related to high-content residual solvents.The second,usually consciously overlooked,is the fluoropolymer's inherent instability against alkaline lithium anodes.Here,we propose indium-based metal-organic frameworks(In-MOFs)as a multifunctional promoter to simultaneously address these two challenges,using poly(vinylidene fluoride-hexafluoropropylene)(PVH)as the typical fluoropolymer.In-MOF plays a trio:(1)adsorbing and converting free residual solvents into bonded states to prevent their side reactions with lithium anodes while retaining their advantages on Li~+transport;(2)forming inorganic-rich solid electrolyte interphase layers to prevent PVH from reacting with lithium anodes and promote uniform lithium deposition without dendrite growth;(3)reducing PVH crystallinity and promoting Li-salt dissociation.Therefore,the resulting PVH/In-MOF(PVH-IM)showcases excellent electrochemical stability against lithium anodes,delivering a 5550 h cycling at 0.2 m A cm^(-2)with a remarkable cumulative lithium deposition capacity of 1110 m Ah cm^(-2).It also exhibits an ultrahighσof 1.23×10^(-3)S cm^(-1)at 25℃.Moreover,all-solid-state LiFePO_4|PVH-IM|Li full cells show outstanding rate capability and cyclability(80.0%capacity retention after 280 cycles at 0.5C),demonstrating high potential for practical ASLMBs.展开更多
Lithium metal batteries (LMBs) show great potential in delivering high energy density (>500 Wh/kg) with cycling [1]. The cycling life of LMBs is mainly improved by regulating the composition and structure of solid/...Lithium metal batteries (LMBs) show great potential in delivering high energy density (>500 Wh/kg) with cycling [1]. The cycling life of LMBs is mainly improved by regulating the composition and structure of solid/cathode electrolyte interphase(SEI/CEI) with electrolytes [2]. However, both Li anode and transition metal oxide cathode have high interfacial reactivity at extreme voltages, which highly needs compatible electrolytes.Recently, localized high-concentration electrolytes (LHCEs) have promisingly stabilized the dual electrodes of high-voltage LMBs[3].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
Lithium-ion batteries(LIBs)are increasingly required to operate under harsh conditions,particularly at low-temperature condition.Developing novel electrolytes is a facile and effective approach to elevate the electroc...Lithium-ion batteries(LIBs)are increasingly required to operate under harsh conditions,particularly at low-temperature condition.Developing novel electrolytes is a facile and effective approach to elevate the electrochemical performances of LIBs at low temperature.Herein,a dual-salt electrolyte consisting of(lithium bis(trifluoromethanesulfonyl)imide(Li TFSI)and lithium difluoro(oxalato)borate(Li ODFB))is proposed to regulate the solvation structure of Li^(+) ions and improve the reaction kinetics under low temperature.Based on the comprehensive electrochemical tests and theoretical computations,the introduction of LiODFB component not only effectively benefits the formation of cathode electrolyte interface(CEI)layer on the surface of LiFePO_(4) electrode,but also inhibits the chemical corrosion effect of Li TFSIcontaining electrolytes on Al foil.As expected,the optimized Li||LiFePO_(4) cells can display high reversible capacity of 117.0 m Ah/g after 100 cycles at-20℃.This work provides both theoretical basis and experimental guidance for the rational design of low-temperature resistant electrolytes.展开更多
Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) ...Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) with weak solvation structures is established by the multi-anion strategy.Multiple anions in the electrolyte strengthen the anion-solvent interactions through stronger ion–dipole interactions.This reduces the quantity of free solvent and improves the reduction resistance of solvents.In addition,the Li ion–solvent interaction is weakened,facilitating the anions to enter the solvation sheaths of Li ions.This multi-anion-dominated weak solvation structures boost Li ion diffusion in the electrolyte,accelerate the desolvation process of Li ions,and induce inorganic-rich solid electrolyte interphase and uniform Li deposition.An average Coulombic efficiency of 99.1%for repeated Li plating/stripping can be achieved.Li||LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cells with a high cathode loading of 3.0 m A h cm^(-2) can maintain a capacity retention as high as 95% after 150 cycles.This finding provides novel standpoints to modulate the interaction of solvation structures and extend the lifespan of high-energy–density Li metal batteries.展开更多
Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a th...Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles,which seriously limits the actual energy density of sulfide all-solid-state lithium batteries(ASSLBs).Fortunately,the preparation of sulfide-polymer composite solid electrolyte(SPCSE)membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties.In this review,recent progress of SPCSE membranes for ASSLBs is summarized.The classification of components in SPCSE membranes is first introduced briefly.Then,the preparation methods of SPCSE membranes are categorized according to process characteristics,in which the challenges of different methods and their corresponding solutions are carefully reviewed.The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance.Finally,we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.展开更多
The growth of dendrites and the side reactions occurring at the Zn anode pose significant challenges to the commercialization of aqueous Zn-ion batteries(AZIBs). These challenges arise from the inherent conflict betwe...The growth of dendrites and the side reactions occurring at the Zn anode pose significant challenges to the commercialization of aqueous Zn-ion batteries(AZIBs). These challenges arise from the inherent conflict between mass transfer and electrochemical kinetics. In this study, we propose the use of a multifunctional electrolyte additive based on the xylose(Xylo) molecule to address these issues by modulating the solvation structure and electrode/electrolyte interface, thereby stabilizing the Zn anode. The introduction of the additive alters the solvation structure, creating steric hindrance that impedes charge transfer and then reduces electrochemical kinetics. Furthermore, in-situ analyses demonstrate that the reconstructed electrode/electrolyte interface facilitates stable and rapid Zn^(2+)ion migration and suppresses corrosion and hydrogen evolution reactions. As a result, symmetric cells incorporating the Xylo additive exhibit significantly enhanced reversibility during the Zn plating/stripping process, with an impressively long lifespan of up to 1986 h, compared to cells using pure ZnSO4electrolyte. When combined with a polyaniline cathode, the full cells demonstrate improved capacity and long-term cyclic stability. This work offers an effective direction for improving the stability of Zn anode via electrolyte design, as well as highperformance AZIBs.展开更多
基金the financial support from the Key Project of Shaanxi Provincial Natural Science Foundation-Key Project of Laboratory(2025SYS-SYSZD-117)the Natural Science Basic Research Program of Shaanxi(2025JCYBQN-125)+8 种基金Young Talent Fund of Xi'an Association for Science and Technology(0959202513002)the Key Industrial Chain Technology Research Program of Xi'an(24ZDCYJSGG0048)the Key Research and Development Program of Xianyang(L2023-ZDYF-SF-077)Postdoctoral Fellowship Program of CPSF(GZC20241442)Shaanxi Postdoctoral Science Foundation(2024BSHSDZZ070)Research Funds for the Interdisciplinary Projects,CHU(300104240913)the Fundamental Research Funds for the Central Universities,CHU(300102385739,300102384201,300102384103)the Scientific Innovation Practice Project of Postgraduate of Chang'an University(300103725063)the financial support from the Australian Research Council。
文摘Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.
基金supported by the National Natural Science Foundation of China(52002297)National Key R&D Program of China(2022VFB2404800)+1 种基金Wuhan Yellow Crane Talents Program,China Postdoctoral Science Foundation(No.2024M752495)the Postdoctoral Fellowship Program of CPSF(No.GZB20230552).
文摘Aqueous alkali metal-ion batteries(AAMIBs)have been recognized as emerging electrochemical energy storage technologies for grid-scale applications owning to their intrinsic safety,cost-effectiveness,and environmental sustainability.However,the practical application of AAMIBs is still severely constrained by the tendency of aqueous electrolytes to freeze at low temperatures and decompose at high temperatures,limiting their operational temperature range.Considering the urgent need for energy systems with higher adaptability and resilience at various application scenarios,designing novel electrolytes via structure modulation has increasingly emerged as a feasible and economical strategy for the performance optimization of wide-temperature AAMIBs.In this review,the latest advancement of wide-temperature electrolytes for AAMIBs is systematically and comprehensively summarized.Specifically,the key challenges,failure mechanisms,correlations between hydrogen bond behaviors and physicochemical properties,and thermodynamic and kinetic interpretations in aqueous electrolytes are discussed firstly.Additionally,we offer forward-looking insights and innovative design principles for developing aqueous electrolytes capable of operating across a broad temperature range.This review is expected to provide some guidance and reference for the rational design and regulation of widetemperature electrolytes for AAMIBs and promote their future development.
基金supported by the University of Wollongong,Wollongong,Australiafinancial support from the National Natural Science Foundation of China(22272086)Natural Science Foundation of Sichuan Province(2023NSFSC0009).
文摘Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy density and improved safety,making them promising alternatives for next-generation rechargeable batteries[1].As a crucial component of these batteries,solid-state electrolytes—divided into inorganic solid ceramic electrolytes(SCEs)and organic solid polymer electrolytes(SPEs)—are vital for lithium-ion transport and inhibiting lithium dendrite growth.Among them,SCEs exhibit high ionic conductivity,excellent mechanical properties,and outstanding electrochemical and thermal stability.Nevertheless,their brittleness,interfacial challenges with electrodes,and the requirement for high stacking pressure during battery operation significantly hinder their scalable application.In comparison,SPEs are more favourable for manufacturing due to their flexibility and good interfacial compatibility with electrodes[2].Despite these advantages,SPEs still face significant challenges in achieving practical application.Firstly,typical SPEs,such as poly(ethylene oxide)(PEO),poly(vinylidene fluoride)(PVDF),and poly(ethylene glycol)diacrylate(PEGDA),are characterized by high crystallinity,which causes polymer chains to be tightly packed and rigid.This restricts the segmental motion within the SPEs,resulting in low ionic conductivity.Secondly,compared to lithium ions,anions with large ionic radii and low charge density typically form weaker interactions with the polymer chains,which facilitates their mobility and results in a low lithium-ion transference number(tt).Thirdly,the weak interactions between polymer chains in typical SPEs lead to a low elastic modulus,which in turn compromises their poor mechanical strength.
基金financially supported by Shenzhen Science and Technology Program(JCYJ20240813142900001)Guangdong Provincial Key Laboratory of New Energy Materials Service Safety。
文摘Chloride-based solid electrolytes are considered promising candidates for next-generation high-energy-density all-solid-state batteries(ASSBs).However,their relatively low oxidative decomposition threshold(~4.2 V vs.Li^(+)/Li)constrains their use in ultrahighvoltage systems(e.g.,4.8 V).In this work,ferroelectric Ba TiO_(3)(BTO)nanoparticles with optimized thickness of~50-100 nm were successfully coated onto Li_(2.5)Y_(0.5)Zr_(0.5)Cl_(6)(LYZC@5BTO)electrolytes using a time-efficient ball-milling process.The nanoparticle-induced interfacial ionic conduction enhancement mechanism contributed to the preservation of LYZC’s high ionic conductivity,which remained at 1.06 m S cm^(-1)for LYZC@5BTO.Furthermore,this surface electric field engineering strategy effectively mitigates the voltage-induced self-decomposition of chloride-based solid electrolytes,suppresses parasitic interfacial reactions with single-crystal NCM811(SCNCM811),and inhibits the irreversible phase transition of SCNCM811.Consequently,the cycling stability of LYZC under high-voltage conditions(4.8 V vs.Li+/Li)is significantly improved.Specifically,ASSB cells employing LYZC@5BTO exhibited a superior discharge capacity of 95.4 m Ah g^(-1)over 200 cycles at 1 C,way outperforming cell using pristine LYZC that only shows a capacity of 55.4 m Ah g^(-1).Furthermore,time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy analysis revealed that Metal-O-Cl by-products from cumulative interfacial side reactions accounted for 6% of the surface species initially,rising to 26% after 200 cycles in pristine LYZC.In contrast,LYZC@5BTO limited this increase to only 14%,confirming the effectiveness of BTO in stabilizing the interfacial chemistry.This electric field modulation strategy offers a promising route toward the commercialization of high-voltage solid-state electrolytes and energy-dense ASSBs.
基金the financial support from the National Natural Science Foundation of China(52203123 and 52473248)State Key Laboratory of Polymer Materials Engineering(sklpme2024-2-04)+1 种基金the Fundamental Research Funds for the Central Universitiessponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.
基金supported by the National Natural Science Foundation of China (Nos. 22379121, 62005216)Basic Public Welfare Research Program of Zhejiang (No. LQ22F050013)+1 种基金Zhejiang Province Key Laboratory of Flexible Electronics Open Fund (2023FE005)Shenzhen Foundation Research Program (No. JCYJ20220530112812028)。
文摘Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fiuorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital(LUMO), which leads to significant consumption of the fiuorinated components upon cycling.Herein, attenuating reductive decomposition of fiuorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate(VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fiuoroethylene carbonate(FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fiuorinated electrolytes in high-voltage Li-metal batteries.
文摘1.Introduction.The ever-increasing demands for high-energy-density power supply systems have driven the rapid development of conventional lithium-ion batteries,of which properties are approaching to the ceiling.In the meantime,the safety of lithium-ion batteries also grabs more attention as their wide application in consumer electronics and electric vehicles.The safety of battery system can be enhanced inherently by replacing the flammable liquid electrolytes with inorganic solid electrolytes,which makes solid-state battery one of the most promising candidates of next-generation energy storage systems[1-3].Additionally,the improvements in energy density are foreseen as solid electrolytes enable lithium metal anode[4-11]and high-voltage cathodes[12-15].
文摘The constant increase in global energy demand and stricter environmental standards are calling for advanced energy storage technologies that can store electricity from intermittent renewable sources such as wind,solar,and tidal power,to allow the broader implementation of the renewables.The gridoriented sodium-ion batteries,potassium ion batteries and multivalent ion batteries are cheaper and more sustainable alternatives to Li-ion,although they are still in the early stages of development.Additional optimisation of these battery systems is required,to improve the energy and power density,and to solve the safety issues caused by dendrites growth in anodes.Electrolyte,one of the most critical components in these batteries,could significantly influence the electrochemical performances and operations of batteries.In this review,the definitions and influences of three critical components(salts,solvents,and additives)in electrolytes are discussed.The significant advantages,challenges,recent progress and future optimisation directions of various electrolytes for monovalent and multivalent ions batteries(i.e.organic,ionic liquid and aqueous liquid electrolytes,polymer and inorganic solid electrolytes)are summarised to guide the practical application for grid-oriented batteries.
基金financial support from the National Natural Science Foundation of China(52203123)the Sichuan Science and Technology Program(2023NSFSC0991)+2 种基金the State Key Laboratory of Polymer Materials Engineering(sklpme 2023-1-05 and sklpme 2024-2-04)the Fundamental Research Funds for the Central Universitiespartially sponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Solvation structures fundamentally control the ion-transport dynamics and mechanical properties of polymer electrolytes.However,there is a lack of strategies to rationally regulate the solvation structures and fundamental understanding on how they control the electrochemical performances.Herein,by harnessing the electrostatic adsorption of one-dimensional nanofiller(i.e.,surface-charged halloysite nanotubes,d-HNTs),we successfully fabricate a high-performance polymer nanocomposite electrolyte enabled by strong surface adsorption,referred as adsorption-state polymer electrolyte(ASPE).This ASPE shows fast ion transport(0.71±0.05 mS cm^(-1)at room temperature),high mechanical strength and toughness(10.3±0.05 MPa;15.73 MJ m^(-3)),improved lithium-ion transference number,and long cycle life with lithium metal anode,in comparison with the sample without the d-HNT adsorption effect.To fundamentally understand these high performances,an anion-rich asymmetric solvent structure model is further proposed and evidenced by both experiments and simulation studies.Results show that the electrostatic adsorption among the d-HNT,ionic liquid electrolyte,and polymer chain generates a nano filler-supported fast ion-conduction pathway with asymmetric Li+-coordination microenvironment.Meanwhile,the anion-rich asymmetric solvent structure model of ASPE also generates a fast de-solvation and anion-derived stable solid-electrolyte interphase for lithium metal anode.The high performance and understanding of the mechanism for ASPE provide a promising path to develop advanced polymer electrolytes.
基金supported by the National Natural Science Foundation of China(Nos.52172214,52272221,52171182)the Postdoctoral Innovation Project of Shandong Province(No.202102003)+2 种基金The Key Research and Development Program of Shandong Province(2021ZLGX01)the Qilu Young Scholar ProgramHPC Cloud Platform of Shandong University are also thanked.
文摘The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.
基金the financial support from the National Key R&D Program of China (Grant No. 2021YFB3800300)the supports from National Key R&D Program of China (Grant No. 2022YFB3807700)+6 种基金the National Natural Science Foundation of China (Grant No. U20A20248)the supports from the National Natural Science Foundation of China (Grant Nos. W2441017, 22409103)the “Innovation Yongjiang 2035” Key R&D Program (Grant Nos. 2024Z040, 2025Z063)the National Key R&D Program of China (Grant No. 2023YFC2812700)the Natural Science Foundation of Shandong Province (Grant No. ZR2024YQ008)funding supports from the National Key R&D Program of China (Grant No. 2021YFB3800300)science and technology innovation fund for emission peak and carbon neutrality of Jiangsu province (Grant Nos. BK20220034, BK20231512)。
文摘With the widespread adoption of lithium-ion batteries(LIBs),safety concerns associated with flammable organic elec-trolytes have become increasingly critical.Solid-state lithium batteries(SSLBs),with enhanced safety and higher energy density potential,are regarded as a promising next-generation energy storage technology.However,the practical appli-cation of solid-state electrolytes(SSEs)remains hindered by several challenges,including low Li+ion conductivity,poor interfacial compatibility with electrodes,unfavorable mechanical properties and difficulties in scalable manufacturing.This review systematically examines recent progress in SSEs,including inorganic types(oxides,sulfides,halides),organic types(polymers,plastic crystals,poly(ionic liquids)(PILs)),and the emerging class of soft solid-state electrolytes(S3Es),especially those based on“rigid-flexible synergy”composites and“Li+-desolvation”mechanism using porous frameworks.Critical assessment reveals that single-component SSEs face inherent limitations that are difficult to be fully overcome through compositional and structural modification alone.In contrast,S3Es integrate the strength of complementary components to achieve a balanced and synergic enhancement in electrochemical properties(e.g.,ionic conductivity and stability window),mechanical integrity,and processability,showing great promise as next-generation SSEs.Furthermore,the application-ori-ented challenges and emerging trends in S3E research are outlined,aiming to provide strategic insights into future develop-ment of high-performance SSEs.
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the financial support from the 261 Project of MIITNatural Science Foundation of Jiangsu Province(No.BK20240179)。
文摘Fluoropolymers promise all-solid-state lithium metal batteries(ASLMBs)but suffer from two critical challenges.The first is the trade-off between ionic conductivity(σ)and lithium anode reactions,closely related to high-content residual solvents.The second,usually consciously overlooked,is the fluoropolymer's inherent instability against alkaline lithium anodes.Here,we propose indium-based metal-organic frameworks(In-MOFs)as a multifunctional promoter to simultaneously address these two challenges,using poly(vinylidene fluoride-hexafluoropropylene)(PVH)as the typical fluoropolymer.In-MOF plays a trio:(1)adsorbing and converting free residual solvents into bonded states to prevent their side reactions with lithium anodes while retaining their advantages on Li~+transport;(2)forming inorganic-rich solid electrolyte interphase layers to prevent PVH from reacting with lithium anodes and promote uniform lithium deposition without dendrite growth;(3)reducing PVH crystallinity and promoting Li-salt dissociation.Therefore,the resulting PVH/In-MOF(PVH-IM)showcases excellent electrochemical stability against lithium anodes,delivering a 5550 h cycling at 0.2 m A cm^(-2)with a remarkable cumulative lithium deposition capacity of 1110 m Ah cm^(-2).It also exhibits an ultrahighσof 1.23×10^(-3)S cm^(-1)at 25℃.Moreover,all-solid-state LiFePO_4|PVH-IM|Li full cells show outstanding rate capability and cyclability(80.0%capacity retention after 280 cycles at 0.5C),demonstrating high potential for practical ASLMBs.
文摘Lithium metal batteries (LMBs) show great potential in delivering high energy density (>500 Wh/kg) with cycling [1]. The cycling life of LMBs is mainly improved by regulating the composition and structure of solid/cathode electrolyte interphase(SEI/CEI) with electrolytes [2]. However, both Li anode and transition metal oxide cathode have high interfacial reactivity at extreme voltages, which highly needs compatible electrolytes.Recently, localized high-concentration electrolytes (LHCEs) have promisingly stabilized the dual electrodes of high-voltage LMBs[3].
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the financial support from the S&T program of Hebei(Nos.215A4401D and 225A4404D)the Collaborative Innovation Center of Marine Science and Technology of Hainan University(No.XTCX2022HYC14)+3 种基金the Fundamental Research Funds for the Hebei University(No.2021YWF11)the Science Research Project of Hebei Education Department(No.QN2024087)the Xingtai City Natural Science Foundation(No.2023ZZ027)partially supported by the Pico Election Microscopy Center of Hainan University。
文摘Lithium-ion batteries(LIBs)are increasingly required to operate under harsh conditions,particularly at low-temperature condition.Developing novel electrolytes is a facile and effective approach to elevate the electrochemical performances of LIBs at low temperature.Herein,a dual-salt electrolyte consisting of(lithium bis(trifluoromethanesulfonyl)imide(Li TFSI)and lithium difluoro(oxalato)borate(Li ODFB))is proposed to regulate the solvation structure of Li^(+) ions and improve the reaction kinetics under low temperature.Based on the comprehensive electrochemical tests and theoretical computations,the introduction of LiODFB component not only effectively benefits the formation of cathode electrolyte interface(CEI)layer on the surface of LiFePO_(4) electrode,but also inhibits the chemical corrosion effect of Li TFSIcontaining electrolytes on Al foil.As expected,the optimized Li||LiFePO_(4) cells can display high reversible capacity of 117.0 m Ah/g after 100 cycles at-20℃.This work provides both theoretical basis and experimental guidance for the rational design of low-temperature resistant electrolytes.
基金funded by National Natural Science Foundation of China (22379072, 92372111, 22179070)the Startup Foundation for Introducing Talent of NUIST (2022r038)+1 种基金the Jiangsu Specially Appointed Professor Program, the Natural Science Foundation of Jiangsu Province (BK20220073)the Fundamental Research Funds for the Central Universities (RF1028623157)。
文摘Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) with weak solvation structures is established by the multi-anion strategy.Multiple anions in the electrolyte strengthen the anion-solvent interactions through stronger ion–dipole interactions.This reduces the quantity of free solvent and improves the reduction resistance of solvents.In addition,the Li ion–solvent interaction is weakened,facilitating the anions to enter the solvation sheaths of Li ions.This multi-anion-dominated weak solvation structures boost Li ion diffusion in the electrolyte,accelerate the desolvation process of Li ions,and induce inorganic-rich solid electrolyte interphase and uniform Li deposition.An average Coulombic efficiency of 99.1%for repeated Li plating/stripping can be achieved.Li||LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cells with a high cathode loading of 3.0 m A h cm^(-2) can maintain a capacity retention as high as 95% after 150 cycles.This finding provides novel standpoints to modulate the interaction of solvation structures and extend the lifespan of high-energy–density Li metal batteries.
基金supported by grants from the National Natural Science Foundation of China(Nos.52072136,52172229,52272201,52302303,51972257)Yanchang Petroleum-WHUT Joint Program(No.yc-whlg-2022ky-05)Fundamental Research Funds for the Central Universities(Nos.104972024RSCrc0006,2023IVA106)for financial support。
文摘Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles,which seriously limits the actual energy density of sulfide all-solid-state lithium batteries(ASSLBs).Fortunately,the preparation of sulfide-polymer composite solid electrolyte(SPCSE)membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties.In this review,recent progress of SPCSE membranes for ASSLBs is summarized.The classification of components in SPCSE membranes is first introduced briefly.Then,the preparation methods of SPCSE membranes are categorized according to process characteristics,in which the challenges of different methods and their corresponding solutions are carefully reviewed.The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance.Finally,we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.
文摘The growth of dendrites and the side reactions occurring at the Zn anode pose significant challenges to the commercialization of aqueous Zn-ion batteries(AZIBs). These challenges arise from the inherent conflict between mass transfer and electrochemical kinetics. In this study, we propose the use of a multifunctional electrolyte additive based on the xylose(Xylo) molecule to address these issues by modulating the solvation structure and electrode/electrolyte interface, thereby stabilizing the Zn anode. The introduction of the additive alters the solvation structure, creating steric hindrance that impedes charge transfer and then reduces electrochemical kinetics. Furthermore, in-situ analyses demonstrate that the reconstructed electrode/electrolyte interface facilitates stable and rapid Zn^(2+)ion migration and suppresses corrosion and hydrogen evolution reactions. As a result, symmetric cells incorporating the Xylo additive exhibit significantly enhanced reversibility during the Zn plating/stripping process, with an impressively long lifespan of up to 1986 h, compared to cells using pure ZnSO4electrolyte. When combined with a polyaniline cathode, the full cells demonstrate improved capacity and long-term cyclic stability. This work offers an effective direction for improving the stability of Zn anode via electrolyte design, as well as highperformance AZIBs.
