The electrolyte directly contacts the essential parts of a lithium-ion battery,and as a result,the electrochemical properties of the electrolyte have a significant impact on the voltage platform,charge discharge capac...The electrolyte directly contacts the essential parts of a lithium-ion battery,and as a result,the electrochemical properties of the electrolyte have a significant impact on the voltage platform,charge discharge capacity,energy density,service life,and rate discharge performance.By raising the voltage at the charge/discharge plateau,the energy density of the battery is increased.However,this causes transition metal dissolution,irreversible phase changes of the cathode active material,and parasitic electrolyte oxidation reactions.This article presents an overview of these concerns to provide a clear explanation of the issues involved in the development of electrolytes for high-voltage lithium-ion batteries.Additionally,solidstate electrolytes enable various applications and will likely have an impact on the development of batteries with high energy densities.It is necessary to improve the high-voltage performance of electrolytes by creating solvents with high thermal stabilities and high voltage resistance and additives with superior film forming performance,multifunctional capabilities,and stable lithium salts.To offer suggestions for the future development of high-energy lithium-ion batteries,we conclude by offering our own opinions and insights on the current development of lithium-ion batteries.展开更多
Further enhancement in the energy density of rechargeable lithium batteries calls for high-voltage cathode materials and stable anodes,as well as matched high-voltage electrolytes without compromising the overall prop...Further enhancement in the energy density of rechargeable lithium batteries calls for high-voltage cathode materials and stable anodes,as well as matched high-voltage electrolytes without compromising the overall property of batteries.Sulfone-based electrolytes have aroused great interest in recent years owing to their wide electrochemical window and high safety.However,significant challenges such as the complexity of synthesis,high melting point(typically above room temperature),high viscosity,and their poor compatibility with graphite-based anodes have drastically impeded their practical applications.In this review,recent progress of sulfone solvents in high energy density rechargeable lithium batteries is summarized theoretically and experimentally.More importantly,general improvement methods of sulfone-based electrolytes,such as adding additives and cosolvents,structural modifications of sulfo ne,superconcentrated salt strategy are briefly discussed.We expect that this review provides inspiration for the future developments of sulfone-based high-voltage electrolytes(SHVEs)and their widespread applications in high specific energy lithium batteries.展开更多
Solid-state batteries(SSBs) are highly attractive on account of their high energy density and good safety.In high-voltage and high-current conditions,however,the interface reactions,structural changes,and decompositio...Solid-state batteries(SSBs) are highly attractive on account of their high energy density and good safety.In high-voltage and high-current conditions,however,the interface reactions,structural changes,and decomposition of the electrolyte impede the transmission of lithium ions in all-solid-state lithium batteries(ASSLBs),significantly reducing the charging and discharging capacity and cycling stability of the battery and therefore restricting its practical applications.The main content of review is to conduct an in-depth analysis of the existing problems of solid-state batteries from the aspects of interface reactions,material failure,ion migration,and dendrite growth,and points out the main factors influencing the electrochemical performance of ASSLBs.Additionally,the compatibility and ion conduction mechanisms between polymer electrolytes,inorganic solid electrolytes,and composite electrolytes and the electrode materials are discussed.Furthermore,the perspectives of electrode materials,electrolyte properties,and interface modification are summarized and prospected,providing new optimization directions for the future commercialization of high-voltage solid-state electrolytes.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
Solid-state lithium batteries have become a research hotspot in the field of large-scale energy storage due to their excellent safety performance.The development of high-voltage positive electrode materials matched wi...Solid-state lithium batteries have become a research hotspot in the field of large-scale energy storage due to their excellent safety performance.The development of high-voltage positive electrode materials matched with lithium metal anode have advanced the energy density of solid-state lithium batteries close to or even exceeding that of lithium batteries based on a liquid electrolyte,which is expected to be commercialized in the future.However,in high voltage conditions(>4.3 V),the decomposition of electrolyte components,structural degradation,and interface side reactions significantly reduce battery performance and hinder its further development.This review summarizes the latest research progress of inorganic electrolytes,polymer electrolytes,and composite electrolytes in high-voltage solid-state lithium batteries.At the same time,the designs of high-voltage polymer gel electrolyte and high-voltage quasi solid-state electrolyte are introduced in detail.In addition,interface engineering is crucial for improving the overall performance of high-voltage solid-state batteries.Finally,we highlight the challenges faced by high-voltage solid-state lithium batteries and put forward our own views on future research directions.This review offers instructive insights into the advancement of high-voltage solid-state lithium batteries for large-scale energy storage applications.展开更多
High-voltage solid-state lithium-ion batteries(SSLIBs)have attracted considerable research attention in recent years due to their high-energy-density and superior safety characteristics.However,the integration of high...High-voltage solid-state lithium-ion batteries(SSLIBs)have attracted considerable research attention in recent years due to their high-energy-density and superior safety characteristics.However,the integration of high-voltage cathodes with solid electrolytes(SEs)presents multiple challenges,including the formation of high-impedance layers from spontaneous chemical reactions,electrochemical instability,insufficient interfacial contact,and lattice expansion.These issues significantly impair battery performance and potentially lead to battery failure,thus impeding the commercialization of high-voltage SSLIBs.The incorporation of fluorides,known for their robust bond strength and high free energy of formation,has emerged as an effective strategy to address these challenges.Fluorinated electrolytes and electrode/electrolyte interfaces have been demonstrated to significantly influence the reaction reversibility/kinetics,safety,and stability of rechargeable batteries,particularly under high voltage.This review summarizes recent advancements in fluorination treatment for high-voltage SEs,focusing on solid polymer electrolytes(SPEs),inorganic solid electrolytes(ISEs),and composite solid electrolytes(CSEs),along with the performance enhancements these strategies afford.This review aims to provide a comprehensive understanding of the structure-property relationships,the characteristics of fluorinated interfaces,and the application of fluorinated SEs in high-voltage SSLIBs.Further,the impacts of residual moisture and the challenges of fluorinated SEs are discussed.Finally,the review explores potential future directions for the development of fluorinated SSLIBs.展开更多
Immense attention has been focused on developing supercapacitors in the field of energy storage by virtue of their exceptional power density,extended cycling stability and operational safety.However,traditional liquid...Immense attention has been focused on developing supercapacitors in the field of energy storage by virtue of their exceptional power density,extended cycling stability and operational safety.However,traditional liquid electrolytes pose severe challenges in response to leakage,high volatility and low electrochemical stability issues.To address these problems,we have developed a novel composite polymer membrane for gel polymer electrolytes(GPEs).This membrane features an internal fibrous framework composed of shape-memory polymers,while surface dielectric layers of PVDF-HFP cross-linked with modified TiO_(2)nanoparticles are constructed on both sides of the framework.This configuration modulates the Stern layer potential gradient and diffuse layer ionic distribution through dielectric polarization,thereby suppressing electrolyte decomposition at high voltages,mitigating side reactions and facilitating ionic conduction.The resultant quasi-solid-state supercapacitor demonstrates excellent electrochemical stability at a voltage of 3.5 V,achieving an energy density of 43.87 Wh kg^(-1),with a high-power density of 22.66 kW kg^(-1)along with exceptional cyclic stability and mechanical flexibility.The synergistic structural design offers a safe and efficient energy harvesting solution for wearable electronic devices and portable energy storage systems.展开更多
Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified W...Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified WSE for fast-charging high-voltage LMBs,which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(TTE)into the tetrahydropyran(THP)based WSE.A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP,which accelerates the de-solvation kinetics of Li~+.Besides,more anions are involved in solvation structure in the presence of TTE,yielding inorganic-rich interphases with improved stability.Li(30μm)||Li Ni_(0.5)Co_(0.2)Mn_(0.3)O_(2)(4.1 mAh/cm^(2))batteries with the TTE modified WSE retain over 64%capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V,much better than that with pure THP based WSE.This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.展开更多
Efficient,safe,and reliable energy output from high-energy-density lithium metal batteries(LMBs)at all climates is crucial for portable electronic devices operating in complex environments.The performance of correspon...Efficient,safe,and reliable energy output from high-energy-density lithium metal batteries(LMBs)at all climates is crucial for portable electronic devices operating in complex environments.The performance of corresponding cathodes and lithium(Li)metal anodes,however,faces significant challenges under such demanding conditions.Herein,a nonflammable electrolyte for high-voltage Li‖LCO cells has been designed,including partially-fluorinated ethyl 4,4,4-trifluorobutyrate(ETFB)as the key solvent,guided by theoretical calculations.With this ETFB-based electrolyte,Li‖LCO cells exhibit enhanced reversible capacities and superior capacity retention at an elevated charge voltage of 4.5 V and a wide operating temperature range spanning from-60℃to 70℃.The cells achieve 67.1%discharge capacity at-60℃,relative to room temperature capacity,and 85.9%100th-cycle retention at 70℃.The outstanding properties are attributed to the LiF-rich interphases formed in the ETFB-based electrolyte with a finetuned solvation structure,in which the coordination environment in the vicinity of Li^(+)cations and the distance between anion and solvents are subtly adjusted by introducing ETFB.This solvation structure has been mutually elucidated through joint spectra characterizations and atomistic simulations.This work presents a new strategy for the design of electrolytes to achieve all-climate reliable and safe application of LMBs.展开更多
Enhancing the energy density of lithium-ion batteries through high-voltage cathodes holds great pro-mise.However,traditional carbonate-based electrolytes face significant challenges due to limited oxida-tive stability...Enhancing the energy density of lithium-ion batteries through high-voltage cathodes holds great pro-mise.However,traditional carbonate-based electrolytes face significant challenges due to limited oxida-tive stability and poor compatibility with high-nickel materials.This study introduces a novel electrolyte that combines bis(triethoxysilyl)methane(DMSP)as the sole solvent with lithium bis(fluorosulfonyl)imide(LiFSI)as the lithium salt.This formulation significantly improves the stability of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes and graphite anodes.The capacity retention of the NCM811 elec-trode increases from 5%to 95%after 1000 cycles at 1 C(3.0-4.5 V),while that of the graphite anode is improved from 22%to 92%after 400 cycles at 0.2 C(0.005-3.0 V).The NCM811//graphite pouch cell exhibits enhanced retention,rising from 12%to 66%at 25℃and from 3%to 65%at 60℃after 300 cycles at 0.2 C.Spectroscopic characterization and theoretical calculations reveal that the steric hindrance of the Si-O-CH_(3)groups in DMSP creates a weakly solvating structure,promoting the formation of Lit^(+)-FSI^(-)ion pairs and aggregation clusters,which enriches the electrode interphase with LiF,Li_(3)N,and Li_(2)SO_(3).Furthermore,DMSP with abundant Si-O effectively enhances the elasticity of the interphase layer,scav-enging harmful substances such as HF and suppressing gas evolution and transition metal dissolution.The simplicity of the DMSP-based electrolyte formulation,coupled with its superior performance,ensures scalability for large-scale manufacturing and practical application in the high-voltage battery.This work provides critical insights into improving interfacial chemistry and addressing compatibility issues in high-voltageNi-rich cathodes.展开更多
Li/Mn-rich layered oxide(LMR)cathode active materials offer remarkably high specific discharge capacity(>250 mAh g^(-1))from both cationic and anionic redox.The latter necessitates harsh charging conditions to high...Li/Mn-rich layered oxide(LMR)cathode active materials offer remarkably high specific discharge capacity(>250 mAh g^(-1))from both cationic and anionic redox.The latter necessitates harsh charging conditions to high cathode potentials(>4.5 V vs Li|Li^(+)),which is accompanied by lattice oxygen release,phase transformation,voltage fade,and transition metal(TM)dissolution.In cells with graphite anode,TM dissolution is particularly detrimental as it initiates electrode crosstalk.Lithium difluorophosphate(LiDFP)is known for its pivotal role in suppressing electrode crosstalk through TM scavenging.In LMR‖graphite cells charged to an upper cutoff voltage(UCV)of 4.5 V,effective TM scavenging effects of LiDFP are observed.In contrast,for an UCV of 4.7 V,the scavenging effects are limited due to more severe TM dissolution compared an UCV of 4.5V.Given the saturation in solubility of the TM scavenging agents,which are LiDFP decomposition products,e.g.,PO_(4)^(3-) and PO_(3)F^(2-),higher concentrations of the LiDFP as precursor"cannot enhance the amount of scavenging species,they rather start to precipitate and damage the anode.展开更多
In-situ polymer electrolytes prepared by Li salt-initiated polymerization are promising electrolytes for solid-state Li metal batteries owing to their enhanced interface contact and facile and green preparation proces...In-situ polymer electrolytes prepared by Li salt-initiated polymerization are promising electrolytes for solid-state Li metal batteries owing to their enhanced interface contact and facile and green preparation process.However,conventional in-situ polymer electrolytes suffer from poor interface stability,low mechanical strength,low oxidation stability,and certain flammability.Herein,a silsesquioxane(POSS)-nanocage-crosslinked in-situ polymer electrolyte(POSS-DOL@PI-F)regulated by fluorinated plasticizer and enhanced by polyimide skeleton is fabricated by Li salt initiated in-situ polymerization.Polyimide skeleton and POSS-nanocage-crosslinked network significantly enhance the tensile strength(22.8 MPa)and thermal stability(200℃)of POSS-DOL@PI-F.Fluorinated plasticizer improves ionic conductivity(6.83×10^(-4)S cm^(-1)),flame retardance,and oxidation stability(5.0 V)of POSS-DOL@PI-F.The fluorinated plasticizer of POSS-DOL@PI-F constructs robust LiF-rich solid electrolyte interphases and cathode electrolyte interphases,thereby dramatically enhancing the interface stability of Li metal anodes and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811)cathodes.POSS-DOL@PI-F enables stable,long-term(1200 h),and dendrite-free cycle of Li‖Li cells.POSS-DOL@PI-F significantly boosts the performance of Li‖NCM811cells,which display superior cycle stability under harsh conditions of high voltage(4.5 V),high temperature(60℃),low temperature(-20℃),and high areal capacity.This work provides a rational design strategy for safe and efficient polymer electrolytes.展开更多
The poor oxidation stability of ether-based solvents has long been a major challenge limiting their practical application.To enhance the oxidative stability of ether-based electrolytes,the physicochemical properties o...The poor oxidation stability of ether-based solvents has long been a major challenge limiting their practical application.To enhance the oxidative stability of ether-based electrolytes,the physicochemical properties of various glycol dimethyl ethers are screened,and diglyme(G2)is selected as the sole solvent for the electrolyte.Lithium bis(fluorosulfonyl)imide(LiFSI),a highly dissociative salt,is used as the primary salt;while lithium nitrate(LiNO_(3))and lithium difluorophosphate(LiDFP),which have small ionic sizes and strong binding energies,are added as secondary salts.The resulting electrolyte can modulate the electric double layer structure by NO_(3)^(-) and DFP^(-) on the cathode side,leading to an increased Liþconcentration that is originally repelled by the cathode.Additionally,the oxidation stability of the electrolyte is improved and the formed electrode-electrolyte interphase is more uniform and stable,thereby enhancing the electrochemical performance of the cells.As a result,cells assembled with a total of 1 M ternary lithium salts in G2 solvent can operate at high voltage of 4.4 V.The LijjNCM811 cells maintain 80.2%capacity retention after 270 cycles at room temperature,with an average Coulombic efficiency of 99.5%,and exhibit 88.4%capacity retention after 200 cycles at -30℃.展开更多
Batteries power numerous technolo-gies,yet higher energy density de-mands push lithium cobalt oxide(Li-CoO_(2)referred as LCO)cathodes to higher voltages,triggering unwanted chemical reactions.In this work,we in-vesti...Batteries power numerous technolo-gies,yet higher energy density de-mands push lithium cobalt oxide(Li-CoO_(2)referred as LCO)cathodes to higher voltages,triggering unwanted chemical reactions.In this work,we in-vestigate how carbonate-based elec-trolytes degrade on deeply delithiated LCO surfaces via extensive reactive molecular dynamics simulations.These simulations unveil the forma-tion of characteristic gas products and unstable surface species,which can undermine the cathode structure and reduce battery performance.By examining different solvent composi-tions,the simulations reveal that partial fluorination reduces oxidative degradation and gas evolution,thus offering a route to improve interface stability.Overall,this study provides an atomic-level perspective on preventing unwanted reactions and guiding the design of safer and more robust battery systems for high-voltage applications.展开更多
Ethylene carbonate(EC)is susceptible to the aggressive chemistry of nickel-rich cathodes,making it undesirable for high-voltage lithium-ion batteries(LIBs).The arbitrary elimination of EC leads to better oxidative tol...Ethylene carbonate(EC)is susceptible to the aggressive chemistry of nickel-rich cathodes,making it undesirable for high-voltage lithium-ion batteries(LIBs).The arbitrary elimination of EC leads to better oxidative tolerance but always incurs interfacial degradation and electrolyte decomposition.Herein,an EC-free electrolyte is deliberately developed based on gradient solvation by pairing solvation-protection agent(1,3,5-trifluorobenzene,F_(3)B)with propylene carbonate(PC)/methyl ethyl carbonate(EMC)formulation.F_(3)B keeps out of inner coordination shell but decomposes preferentially to construct robust interphase,inhibiting solvent decomposition and electrode corrosion.Thereby,the optimized electrolyte(1.1 M)with wide liquid range(-70–77℃)conveys decent interfacial compatibility and high-voltage stability(4.6 V for LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2),NCM622),qualifying reliable operation of practical NCM/graphite pouch cell(81.1%capacity retention over 600 cycles at 0.5 C).The solvation preservation and interface protection from F_(3)B blaze a new avenue for developing high-voltage electrolytes in next-generation LIBs.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
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
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 zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density...Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.展开更多
The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and fla...The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and flammability,as well as performance degradation due to uncontrollable dendrite growth in liquid electrolytes,have been limiting the further development of energy storage devices.In this regard,gel polymer electrolytes(GPEs)based on lignocellulosic(cellulose,hemicellulose,lignin)have attracted great interest due to their high thermal stability,excellent electrolyte wettability,and natural abundance.Therefore,in this critical review,a comprehensive overview of the current challenges faced by GPEs is presented,followed by a detailed description of the opportunities and advantages of lignocellulosic materials for the fabrication of GPEs for energy storage devices.Notably,the key properties and corresponding construction strategies of GPEs for energy storage are analyzed and discussed from the perspective of lignocellulose for the first time.Moreover,the future challenges and prospects of lignocellulose-mediated GPEs in energy storage applications are also critically reviewed and discussed.We sincerely hope this review will stimulate further research on lignocellulose-mediated GPEs in energy storage and provide meaningful directions for the strategy of designing advanced GPEs.展开更多
基金supported by the Shandong Provincial Natural Science Foundation,China(No.ZR2019MEM014)。
文摘The electrolyte directly contacts the essential parts of a lithium-ion battery,and as a result,the electrochemical properties of the electrolyte have a significant impact on the voltage platform,charge discharge capacity,energy density,service life,and rate discharge performance.By raising the voltage at the charge/discharge plateau,the energy density of the battery is increased.However,this causes transition metal dissolution,irreversible phase changes of the cathode active material,and parasitic electrolyte oxidation reactions.This article presents an overview of these concerns to provide a clear explanation of the issues involved in the development of electrolytes for high-voltage lithium-ion batteries.Additionally,solidstate electrolytes enable various applications and will likely have an impact on the development of batteries with high energy densities.It is necessary to improve the high-voltage performance of electrolytes by creating solvents with high thermal stabilities and high voltage resistance and additives with superior film forming performance,multifunctional capabilities,and stable lithium salts.To offer suggestions for the future development of high-energy lithium-ion batteries,we conclude by offering our own opinions and insights on the current development of lithium-ion batteries.
基金the financial support from the Beijing Natural Science Foundation(No.L182023)。
文摘Further enhancement in the energy density of rechargeable lithium batteries calls for high-voltage cathode materials and stable anodes,as well as matched high-voltage electrolytes without compromising the overall property of batteries.Sulfone-based electrolytes have aroused great interest in recent years owing to their wide electrochemical window and high safety.However,significant challenges such as the complexity of synthesis,high melting point(typically above room temperature),high viscosity,and their poor compatibility with graphite-based anodes have drastically impeded their practical applications.In this review,recent progress of sulfone solvents in high energy density rechargeable lithium batteries is summarized theoretically and experimentally.More importantly,general improvement methods of sulfone-based electrolytes,such as adding additives and cosolvents,structural modifications of sulfo ne,superconcentrated salt strategy are briefly discussed.We expect that this review provides inspiration for the future developments of sulfone-based high-voltage electrolytes(SHVEs)and their widespread applications in high specific energy lithium batteries.
基金financial support received from the National Key R&D Program of China (2023YFB2504000)the financial support from the National Outstanding Youth Foundation of China (52125104)+2 种基金the National Natural Science Foundation of China (52071285)the Fundamental Research Funds for the Central Universities (226-2024-00075)the National Youth Top-Notch Talent Support Program。
文摘Solid-state batteries(SSBs) are highly attractive on account of their high energy density and good safety.In high-voltage and high-current conditions,however,the interface reactions,structural changes,and decomposition of the electrolyte impede the transmission of lithium ions in all-solid-state lithium batteries(ASSLBs),significantly reducing the charging and discharging capacity and cycling stability of the battery and therefore restricting its practical applications.The main content of review is to conduct an in-depth analysis of the existing problems of solid-state batteries from the aspects of interface reactions,material failure,ion migration,and dendrite growth,and points out the main factors influencing the electrochemical performance of ASSLBs.Additionally,the compatibility and ion conduction mechanisms between polymer electrolytes,inorganic solid electrolytes,and composite electrolytes and the electrode materials are discussed.Furthermore,the perspectives of electrode materials,electrolyte properties,and interface modification are summarized and prospected,providing new optimization directions for the future commercialization of high-voltage solid-state electrolytes.
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.
基金supported by the National Key R&D Program of China(2024YFA1211100)the National Natural Science Foundation of China(52301278,22479080,52202254,92372001,22393900,and 92372203)+2 种基金the Natural Science Foundation of Jiangsu Province(BK20230937,BK20220966)the Science and Technology Plans of Tianjin(23JCYBJC00170,24JCJQJC00220,and 24ZXZSSS00390)the Fundamental Research Funds for the Central Universities(02063253167,30922010708)。
文摘Solid-state lithium batteries have become a research hotspot in the field of large-scale energy storage due to their excellent safety performance.The development of high-voltage positive electrode materials matched with lithium metal anode have advanced the energy density of solid-state lithium batteries close to or even exceeding that of lithium batteries based on a liquid electrolyte,which is expected to be commercialized in the future.However,in high voltage conditions(>4.3 V),the decomposition of electrolyte components,structural degradation,and interface side reactions significantly reduce battery performance and hinder its further development.This review summarizes the latest research progress of inorganic electrolytes,polymer electrolytes,and composite electrolytes in high-voltage solid-state lithium batteries.At the same time,the designs of high-voltage polymer gel electrolyte and high-voltage quasi solid-state electrolyte are introduced in detail.In addition,interface engineering is crucial for improving the overall performance of high-voltage solid-state batteries.Finally,we highlight the challenges faced by high-voltage solid-state lithium batteries and put forward our own views on future research directions.This review offers instructive insights into the advancement of high-voltage solid-state lithium batteries for large-scale energy storage applications.
基金supported by the A*STAR MTC Programmatic Project(No.M23L9b0052)the Indonesia-NTU Singapore Institute of Research for Sustainability and Innovation(INSPIRASI)(No.6635/E3/KL.02.02/2023)+2 种基金the Singapore NRF Singapore-China Flagship Program(No.023740-00001)the National Natural Science Foundation of China(Nos.11975043 and 11475300)the China Scholarship Council(No.202306460087)。
文摘High-voltage solid-state lithium-ion batteries(SSLIBs)have attracted considerable research attention in recent years due to their high-energy-density and superior safety characteristics.However,the integration of high-voltage cathodes with solid electrolytes(SEs)presents multiple challenges,including the formation of high-impedance layers from spontaneous chemical reactions,electrochemical instability,insufficient interfacial contact,and lattice expansion.These issues significantly impair battery performance and potentially lead to battery failure,thus impeding the commercialization of high-voltage SSLIBs.The incorporation of fluorides,known for their robust bond strength and high free energy of formation,has emerged as an effective strategy to address these challenges.Fluorinated electrolytes and electrode/electrolyte interfaces have been demonstrated to significantly influence the reaction reversibility/kinetics,safety,and stability of rechargeable batteries,particularly under high voltage.This review summarizes recent advancements in fluorination treatment for high-voltage SEs,focusing on solid polymer electrolytes(SPEs),inorganic solid electrolytes(ISEs),and composite solid electrolytes(CSEs),along with the performance enhancements these strategies afford.This review aims to provide a comprehensive understanding of the structure-property relationships,the characteristics of fluorinated interfaces,and the application of fluorinated SEs in high-voltage SSLIBs.Further,the impacts of residual moisture and the challenges of fluorinated SEs are discussed.Finally,the review explores potential future directions for the development of fluorinated SSLIBs.
基金financially supported by the Key Research and Development Program of Shaanxi(No.2022GXLH-01-23)the Fundamental Research Funds for the Central Universities,CHD(No.300102384106)+1 种基金the Innovation Capability Support Program of Shaanxi(No.2022KXJ-144)the National Natural Science Foundation of China(No.22209101)
文摘Immense attention has been focused on developing supercapacitors in the field of energy storage by virtue of their exceptional power density,extended cycling stability and operational safety.However,traditional liquid electrolytes pose severe challenges in response to leakage,high volatility and low electrochemical stability issues.To address these problems,we have developed a novel composite polymer membrane for gel polymer electrolytes(GPEs).This membrane features an internal fibrous framework composed of shape-memory polymers,while surface dielectric layers of PVDF-HFP cross-linked with modified TiO_(2)nanoparticles are constructed on both sides of the framework.This configuration modulates the Stern layer potential gradient and diffuse layer ionic distribution through dielectric polarization,thereby suppressing electrolyte decomposition at high voltages,mitigating side reactions and facilitating ionic conduction.The resultant quasi-solid-state supercapacitor demonstrates excellent electrochemical stability at a voltage of 3.5 V,achieving an energy density of 43.87 Wh kg^(-1),with a high-power density of 22.66 kW kg^(-1)along with exceptional cyclic stability and mechanical flexibility.The synergistic structural design offers a safe and efficient energy harvesting solution for wearable electronic devices and portable energy storage systems.
基金supported by Hengyang City,Hunan Province Science and Technology Innovation Project(No.202250045319)the National Natural Science Foundation of China(Nos.11375084,21808125)the Scientific Research Planning Project of Jilin Provincial Education Department(No.JJKH20241249KJ)。
文摘Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified WSE for fast-charging high-voltage LMBs,which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(TTE)into the tetrahydropyran(THP)based WSE.A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP,which accelerates the de-solvation kinetics of Li~+.Besides,more anions are involved in solvation structure in the presence of TTE,yielding inorganic-rich interphases with improved stability.Li(30μm)||Li Ni_(0.5)Co_(0.2)Mn_(0.3)O_(2)(4.1 mAh/cm^(2))batteries with the TTE modified WSE retain over 64%capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V,much better than that with pure THP based WSE.This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.
基金the financial support from Projects of Science&Technology Department of Sichuan Province(Grant No.22023YFG0082,Grant No.2023YFG0096,and Grant No.2023ZHJY0019)Chengdu Science and Technology Projects(Grant No.2024-YF08-00062-GX).
文摘Efficient,safe,and reliable energy output from high-energy-density lithium metal batteries(LMBs)at all climates is crucial for portable electronic devices operating in complex environments.The performance of corresponding cathodes and lithium(Li)metal anodes,however,faces significant challenges under such demanding conditions.Herein,a nonflammable electrolyte for high-voltage Li‖LCO cells has been designed,including partially-fluorinated ethyl 4,4,4-trifluorobutyrate(ETFB)as the key solvent,guided by theoretical calculations.With this ETFB-based electrolyte,Li‖LCO cells exhibit enhanced reversible capacities and superior capacity retention at an elevated charge voltage of 4.5 V and a wide operating temperature range spanning from-60℃to 70℃.The cells achieve 67.1%discharge capacity at-60℃,relative to room temperature capacity,and 85.9%100th-cycle retention at 70℃.The outstanding properties are attributed to the LiF-rich interphases formed in the ETFB-based electrolyte with a finetuned solvation structure,in which the coordination environment in the vicinity of Li^(+)cations and the distance between anion and solvents are subtly adjusted by introducing ETFB.This solvation structure has been mutually elucidated through joint spectra characterizations and atomistic simulations.This work presents a new strategy for the design of electrolytes to achieve all-climate reliable and safe application of LMBs.
基金supported by the National Natural Science Foundation of China (Grant No. 22179041)the Guangzhou Science and Technology Plan Project (Grant No. 2024A04J4354)the Guangdong Basic and Applied Basic Research Foundation (Grant No. 2024A1515010034)
文摘Enhancing the energy density of lithium-ion batteries through high-voltage cathodes holds great pro-mise.However,traditional carbonate-based electrolytes face significant challenges due to limited oxida-tive stability and poor compatibility with high-nickel materials.This study introduces a novel electrolyte that combines bis(triethoxysilyl)methane(DMSP)as the sole solvent with lithium bis(fluorosulfonyl)imide(LiFSI)as the lithium salt.This formulation significantly improves the stability of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes and graphite anodes.The capacity retention of the NCM811 elec-trode increases from 5%to 95%after 1000 cycles at 1 C(3.0-4.5 V),while that of the graphite anode is improved from 22%to 92%after 400 cycles at 0.2 C(0.005-3.0 V).The NCM811//graphite pouch cell exhibits enhanced retention,rising from 12%to 66%at 25℃and from 3%to 65%at 60℃after 300 cycles at 0.2 C.Spectroscopic characterization and theoretical calculations reveal that the steric hindrance of the Si-O-CH_(3)groups in DMSP creates a weakly solvating structure,promoting the formation of Lit^(+)-FSI^(-)ion pairs and aggregation clusters,which enriches the electrode interphase with LiF,Li_(3)N,and Li_(2)SO_(3).Furthermore,DMSP with abundant Si-O effectively enhances the elasticity of the interphase layer,scav-enging harmful substances such as HF and suppressing gas evolution and transition metal dissolution.The simplicity of the DMSP-based electrolyte formulation,coupled with its superior performance,ensures scalability for large-scale manufacturing and practical application in the high-voltage battery.This work provides critical insights into improving interfacial chemistry and addressing compatibility issues in high-voltageNi-rich cathodes.
基金the Ministry for Culture and Science of North Rhine Westphalia(Germany)for funding this work within the International Graduate School for Battery Chemistry,Characterization,Analysis,Recycling,and Application(BACCARA)Open Access funding enabled and organized by Projekt DEAL。
文摘Li/Mn-rich layered oxide(LMR)cathode active materials offer remarkably high specific discharge capacity(>250 mAh g^(-1))from both cationic and anionic redox.The latter necessitates harsh charging conditions to high cathode potentials(>4.5 V vs Li|Li^(+)),which is accompanied by lattice oxygen release,phase transformation,voltage fade,and transition metal(TM)dissolution.In cells with graphite anode,TM dissolution is particularly detrimental as it initiates electrode crosstalk.Lithium difluorophosphate(LiDFP)is known for its pivotal role in suppressing electrode crosstalk through TM scavenging.In LMR‖graphite cells charged to an upper cutoff voltage(UCV)of 4.5 V,effective TM scavenging effects of LiDFP are observed.In contrast,for an UCV of 4.7 V,the scavenging effects are limited due to more severe TM dissolution compared an UCV of 4.5V.Given the saturation in solubility of the TM scavenging agents,which are LiDFP decomposition products,e.g.,PO_(4)^(3-) and PO_(3)F^(2-),higher concentrations of the LiDFP as precursor"cannot enhance the amount of scavenging species,they rather start to precipitate and damage the anode.
基金supported by the National Natural Science Foundation of China(22375116,22001057)the Science Foundation of High-Level Talents of Wuyi University(2019AL017,2021AL002)Tianjin Lishen Battery Co.,Ltd。
文摘In-situ polymer electrolytes prepared by Li salt-initiated polymerization are promising electrolytes for solid-state Li metal batteries owing to their enhanced interface contact and facile and green preparation process.However,conventional in-situ polymer electrolytes suffer from poor interface stability,low mechanical strength,low oxidation stability,and certain flammability.Herein,a silsesquioxane(POSS)-nanocage-crosslinked in-situ polymer electrolyte(POSS-DOL@PI-F)regulated by fluorinated plasticizer and enhanced by polyimide skeleton is fabricated by Li salt initiated in-situ polymerization.Polyimide skeleton and POSS-nanocage-crosslinked network significantly enhance the tensile strength(22.8 MPa)and thermal stability(200℃)of POSS-DOL@PI-F.Fluorinated plasticizer improves ionic conductivity(6.83×10^(-4)S cm^(-1)),flame retardance,and oxidation stability(5.0 V)of POSS-DOL@PI-F.The fluorinated plasticizer of POSS-DOL@PI-F constructs robust LiF-rich solid electrolyte interphases and cathode electrolyte interphases,thereby dramatically enhancing the interface stability of Li metal anodes and LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811)cathodes.POSS-DOL@PI-F enables stable,long-term(1200 h),and dendrite-free cycle of Li‖Li cells.POSS-DOL@PI-F significantly boosts the performance of Li‖NCM811cells,which display superior cycle stability under harsh conditions of high voltage(4.5 V),high temperature(60℃),low temperature(-20℃),and high areal capacity.This work provides a rational design strategy for safe and efficient polymer electrolytes.
文摘The poor oxidation stability of ether-based solvents has long been a major challenge limiting their practical application.To enhance the oxidative stability of ether-based electrolytes,the physicochemical properties of various glycol dimethyl ethers are screened,and diglyme(G2)is selected as the sole solvent for the electrolyte.Lithium bis(fluorosulfonyl)imide(LiFSI),a highly dissociative salt,is used as the primary salt;while lithium nitrate(LiNO_(3))and lithium difluorophosphate(LiDFP),which have small ionic sizes and strong binding energies,are added as secondary salts.The resulting electrolyte can modulate the electric double layer structure by NO_(3)^(-) and DFP^(-) on the cathode side,leading to an increased Liþconcentration that is originally repelled by the cathode.Additionally,the oxidation stability of the electrolyte is improved and the formed electrode-electrolyte interphase is more uniform and stable,thereby enhancing the electrochemical performance of the cells.As a result,cells assembled with a total of 1 M ternary lithium salts in G2 solvent can operate at high voltage of 4.4 V.The LijjNCM811 cells maintain 80.2%capacity retention after 270 cycles at room temperature,with an average Coulombic efficiency of 99.5%,and exhibit 88.4%capacity retention after 200 cycles at -30℃.
基金support from the National Key Research and Development Program of China(No.2022YFB2502200)the Natural Science Foun-dation of Jiangsu Province(BK20230065)+2 种基金the Key Laboratory of Functional Nano&Soft Materials,the Collaborative Innovation Center of Suzhou Nano Sci-ence&Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the 111 Project,Joint International Research Laboratory of Carbon-Based Functional Materials and Devices,Yue Liu acknowledges support from the National Natural Science Foundation of China(22303058)the Natural Science Foundation of Jiangsu Province(BK20230475).
文摘Batteries power numerous technolo-gies,yet higher energy density de-mands push lithium cobalt oxide(Li-CoO_(2)referred as LCO)cathodes to higher voltages,triggering unwanted chemical reactions.In this work,we in-vestigate how carbonate-based elec-trolytes degrade on deeply delithiated LCO surfaces via extensive reactive molecular dynamics simulations.These simulations unveil the forma-tion of characteristic gas products and unstable surface species,which can undermine the cathode structure and reduce battery performance.By examining different solvent composi-tions,the simulations reveal that partial fluorination reduces oxidative degradation and gas evolution,thus offering a route to improve interface stability.Overall,this study provides an atomic-level perspective on preventing unwanted reactions and guiding the design of safer and more robust battery systems for high-voltage applications.
基金supported by the National Key Research and Development Program of China(No.2022YFB2404800)。
文摘Ethylene carbonate(EC)is susceptible to the aggressive chemistry of nickel-rich cathodes,making it undesirable for high-voltage lithium-ion batteries(LIBs).The arbitrary elimination of EC leads to better oxidative tolerance but always incurs interfacial degradation and electrolyte decomposition.Herein,an EC-free electrolyte is deliberately developed based on gradient solvation by pairing solvation-protection agent(1,3,5-trifluorobenzene,F_(3)B)with propylene carbonate(PC)/methyl ethyl carbonate(EMC)formulation.F_(3)B keeps out of inner coordination shell but decomposes preferentially to construct robust interphase,inhibiting solvent decomposition and electrode corrosion.Thereby,the optimized electrolyte(1.1 M)with wide liquid range(-70–77℃)conveys decent interfacial compatibility and high-voltage stability(4.6 V for LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2),NCM622),qualifying reliable operation of practical NCM/graphite pouch cell(81.1%capacity retention over 600 cycles at 0.5 C).The solvation preservation and interface protection from F_(3)B blaze a new avenue for developing high-voltage electrolytes in next-generation LIBs.
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 Natural Science Foundation of China(Nos.52125202,52202100,and U24A2065)the Natural Science Foundation of Jiangsu Province(BK20243016)Fundamental Research Funds for the Central Universities,China Postdoctoral Science Foundation(No.2024T171166).
文摘Aqueous zinc-ion batteries(AZIBs)have garnered considerable attention as promising post-lithium energy storage technologies owing to their intrinsic safety,cost-effectiveness,and competitive gravimetric energy density.However,their practical commercialization is hindered by critical challenges on the anode side,including dendrite growth and parasitic reactions at the anode/electrolyte interface.Recent studies highlight that rational electrolyte structure engineering offers an effective route to mitigate these issues and strengthen the electrochemical performance of the zinc metal anode.In this review,we systematically summarize state-of-the-art strategies for electrolyte optimization,with a particular focus on the zinc salts regulation,electrolyte additives,and the construction of novel electrolytes,while elucidating the underlying design principles.We further discuss the key structure–property relationships governing electrolyte behavior to provide guidance for the development of next-generation electrolytes.Finally,future perspectives on advanced electrolyte design are proposed.This review aims to serve as a comprehensive reference for researchers exploring high-performance electrolyte engineering in AZIBs.
基金supported by the National Natural Science Foundation of China(32501592,32271814,32301530,32471806)Young Elite Scientist Sponsorship Program by Cast(No.YESS20230242)+3 种基金Natural Science Foundation of Tianjin(23JCZDJC00630,24JCZDJC00630)the China Postdoctoral Science Foundation(2023M740563)Tianjin Enterprise Technology Commissioner Project(25YDTPJC00690)China Scholarship Council(202408120091,202408120105).
文摘The pursuit of high energy density and sustainable energy storage devices has been the target of many researchers.However,safety issues such as the susceptibility of conventional liquid electrolytes to leakage and flammability,as well as performance degradation due to uncontrollable dendrite growth in liquid electrolytes,have been limiting the further development of energy storage devices.In this regard,gel polymer electrolytes(GPEs)based on lignocellulosic(cellulose,hemicellulose,lignin)have attracted great interest due to their high thermal stability,excellent electrolyte wettability,and natural abundance.Therefore,in this critical review,a comprehensive overview of the current challenges faced by GPEs is presented,followed by a detailed description of the opportunities and advantages of lignocellulosic materials for the fabrication of GPEs for energy storage devices.Notably,the key properties and corresponding construction strategies of GPEs for energy storage are analyzed and discussed from the perspective of lignocellulose for the first time.Moreover,the future challenges and prospects of lignocellulose-mediated GPEs in energy storage applications are also critically reviewed and discussed.We sincerely hope this review will stimulate further research on lignocellulose-mediated GPEs in energy storage and provide meaningful directions for the strategy of designing advanced GPEs.
