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
To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified ...To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.展开更多
All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercializat...All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.展开更多
Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature.However,the use of Succinonitrile is l...Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature.However,the use of Succinonitrile is limited due to its corrosion of Li metal.Herein,we report a solid polymer electrolyte with high ionic conductivity(2.17×10^(−3)S cm^(−1),35°C)enhanced by Ti_(3)C_(2)T_(x).Corrosion of the Li anode is prevented due to the Succinonitrile molecules being efficiently anchored by Ti_(3)C_(2)T_(x).Meanwhile,the coordination environment of Li^(+)is weakened due to the introduction of competitive coordination induction effects into the polymer electrolyte,resulting in efficient Li^(+)conduction.Furthermore,the mechanical properties of the electrolyte are enhanced by modulating the ratio of Ti_(3)C_(2)T_(x)to suppress the growth of Li dendrites.Therefore,Li||Li symmetric batteries deliver stable cycling up to 8000 h at 28°C.LiFePO4||Li full batteries exhibit excellent cycling stability of 151.7 mAh g^(−1)with a capacity retention of 99.3%after 300 cycles.This work not only presents a new idea to suppress the corrosion of the Li anode by Succinonitrile but also provides a simple,feasible,and scalable strategy for high-performance Li metal batteries.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
A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses the...A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.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
Quasi-solid-state lithium-metal batteries(QSLMBs)are promising candidates for next-generation battery systems due to their high energy density and enhanced safety.However,their practical application has been hindered ...Quasi-solid-state lithium-metal batteries(QSLMBs)are promising candidates for next-generation battery systems due to their high energy density and enhanced safety.However,their practical application has been hindered by low ionic conductivity and the growth of lithium dendrites.To achieve ordered transport of Li^(+)ions in quasi-solid electrolytes(QSEs),improve ionic conductivity,and homogenize Li^(+)fluxes on the surface of the lithium metal anode(LMA),we propose a novel method.This method involves constructing"ion relay stations"in QSEs by introducing cyano-functionalized boron nitride nanosheets into pentaerythritol tetraacrylate(PETEA)-based polymer electrolytes.The functionalized boron nitride nanosheets promote the dissociation of lithium salts through ion-dipole interactions,optimizing the solvated structure to facilitate the orderly transport of Li+ions,resulting in an ionic conductivity of2.5×10^(-3)S cm^(-1)at 30℃.Notably,this strategy regulates the Li^(+)distribution on the surface of the LMA,effectively inhibiting the growth of lithium dendrites,Li‖Li symmetrical cells using this type of electrolyte maintain stability for over 2000 h at 2 mA cm^(-2)and 2 mAh cm^(-2).Additionally,with a high LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)loading of 8.5 mg cm^(-2),the cells exhibit excellent cycling performance,retaining a high capacity after 400 cycles.This innovative QSE design strategy represents a significant advancement towards the development of high-performance QSLMBs.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
Solid polymer electrolytes have garnered significant attention for lithium batteries because of their flexibility and safety.However,poor ionic conductivity,lithium dendrite formation,and high impedance hinder their p...Solid polymer electrolytes have garnered significant attention for lithium batteries because of their flexibility and safety.However,poor ionic conductivity,lithium dendrite formation,and high impedance hinder their practical application.In this study,a thin,flexible,3D hybrid solid electrolyte(3DHSE)is prepared by in situ thermal cross-linking polymerization with electrospun 3D nanowebs.The 3DHSE comprises Al-doped Li_(7)La_(3)Zr_(2)O_(12)(ALLZO)embedded in electrospun poly(vinylidene fluoride-cohexafluoropropylene)(PVDF-HFP)nonwoven 3D nanowebs and an in situ cross-linked polyethylene oxide(PEO)-based solid polymer electrolyte.The 3DHSE exhibits high tensile strength(6.55 MPa),a strain of 40.28%,enhanced ionic conductivity(7.86×10^(-4) S cm^(-1)),and a superior lithium-ion transference number(0.76)to that of the PVDF-HFP-based solid polymer electrolyte(PSPE).This enables highly stable lithium plating/stripping cycling for over 900 h at 25℃ with a current density of 0.2 mA cm^(-2).The LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811)/3DHSE/Li cell has a higher capacity(140.56 mAh g^(-1) at 0.1 C)than the NCM811/PSPE/Li cell(124.88 mAh g^(-1) at 0.1 C)at 25℃.The 3DHSE enhances mechanical properties,stabilizes interfacial contact,improves ion transport,prevents NCM811 cracking,and significantly boosts cycling performance.This study highlights the potential of the 3DHSE as a candidate for advanced lithium polymer battery technology.展开更多
Li-argyrodites are promising solid electrolytes(SEs)for solid-state Li-ion batteries(SSLBs),but their large-scale industrial application remains a challenge.Conventional synthesis methods for SEs suffer from long reac...Li-argyrodites are promising solid electrolytes(SEs)for solid-state Li-ion batteries(SSLBs),but their large-scale industrial application remains a challenge.Conventional synthesis methods for SEs suffer from long reaction times and high energy consumption.In this study,we present a wet process for the synthesis of halogen-rich argyrodite Li_(6-a)PS_(5-a)Cl_(1+a)precursors(LPSCl_(1+a)-P,a=0–0.7)via an energysaving microwave-assisted process.Utilizing vibrational heating,we accelerate the formation of Liargyrodite precursor,even at excessive Cl-ion concentration,which significantly shortens the reaction time compared to traditional methods.After crystallization,we successfully synthesize the Liargyrodite,Li_(5.5)PS_(4.5)Cl_(1.5),which exhibits the superior ionic conductivity(7.8 mS cm^(-1))and low activation energy(0.23 eV)along with extremely low electric conductivity.The Li_(5.5)PS_(4.5)Cl_(1.5)exhibits superior Li compatibility owing to its high reversible striping/plating ability(over 5000 h)and high current density acceptability(1.3 mA cm^(-2)).It also exhibits excellent cycle reversibility and rate capability with NCM622 cathode(148.3 mA h g^(-1)at 1 C for 100 cycles with capacity retention of 85.6%).This finding suggests a potentially simpler and more scalable synthetic route to produce high-performance SEs.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
This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Proces...This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Process(CSP).By optimizing the sintering pressure,it is achieved an intimate contact between the cathode and the solid electrolyte,leading to an enhanced electrochemical performance.Bilayers cold sintered at 300 MPa and a low-sintering temperature of 150℃exhibit high ionic conductivities(0.5 mS cm^(-1))and stable specific capacities at room temperature(160.1 mAh g^(-1)LFP at C/10 and 75.8 mAh g^(-1)_(LFP)at 1 C).Moreover,an operando electrochemical impedance spectroscopy(EIS)technique is employed to identify limiting factors of the bilayer kinetics and to anticipate the overall electrochemical behavior.Results suggest that capacity fading can occur in samples prepared with high sintering pressures due to a volume reduction in the LFP crystalline cell.This work demonstrates the potential of CSP to produce straightforward high-performance bilayers and introduces a valuable non-destructive instrument for understanding and avoiding degradation in solid-state lithium-based batteries.展开更多
Compared to traditional liquid electrolyte batteries,solid metal batteries offer advantages such as a wide operating temperature range,high energy density,and improved safety,making them a promising energy storage tec...Compared to traditional liquid electrolyte batteries,solid metal batteries offer advantages such as a wide operating temperature range,high energy density,and improved safety,making them a promising energy storage technology.Solid electrolytes,as the core components of solid‐state batteries,are key factors in advancing solid‐state battery technology.Among various solid electrolytes,Na super ionic conductor(NASICON)‐type solid electrolytes exhibit high ionic conductivity(10−3 S·cm−1),a wide electrochemical window,and good thermal stability,providing room for the development of high energy‐density solid metal batteries.Since the discovery of NASICON‐type solid electrolytes in 1976,interest in their use in all‐solid‐state battery development has grown significantly.In this review,we comprehensively analyze the common features of NASICON lithium‐ion conductors and NASICON sodium‐ion conductors,review the historical development of NASICON‐type solid electrolytes,systematically summarize the transport mechanisms of metal cations in NASICON‐type solid electrolytes,discuss the latest strategies for enhancing ionic conductivity,elaborate on the latest methods for improving mechanical stability and interface stability,and point out the requirements of high energy density devices for NASICON‐type solid electrolytes as well as three types of in situ characterization techniques for interfaces.Finally,we highlight the challenges and potential solutions for the future development of NASICON‐type solid electrolytes and solid‐state metal batteries.展开更多
Garnet Li_(7)La_(3)Zr_(2)O_(12)(LLZO)electrolytes have been recognized as a promising candidate to replace liquid/molten-state electrolytes in battery applications due to their exceptional performance,particularly Ga-...Garnet Li_(7)La_(3)Zr_(2)O_(12)(LLZO)electrolytes have been recognized as a promising candidate to replace liquid/molten-state electrolytes in battery applications due to their exceptional performance,particularly Ga-doped LLZO(LLZGO),which exhibits high ionic conductivity.However,the limited size of the Liþtransport bottleneck restricts its high-current discharging performance.The present study focuses on the synthesis of Ga^(3+)þand Ba^(2+)þco-doped LLZO(LLZGBO)and investigates the influence of doping contents on the morphology,crystal structure,Liþtransport bottleneck size,and ionic conductivity.In particular,Ga_(0.32)Ba_(0.15)exhibits the highest ionic conductivity(6.11E-2 S cm^(-1) at 550 C)in comparison with other compositions,which can be attributed to its higher-energy morphology,larger bottleneck and unique Liþtransport channel.In addition to Ba^(2+),Sr^(2+)þand Ca^(2+)have been co-doped with Ga3þinto LLZO,respectively,to study the effect of doping ion radius on crystal structures and the properties of electrolytes.The characterization results demonstrate that the easier Liþtransport and higher ionic conductivity can be obtained when the electrolyte is doped with larger-radius ions.As a result,the assembled thermal battery with Ga_(0.32)Ba_(0.15)-LLZO electrolyte exhibits a remarkable voltage platform of 1.81 V and a high specific capacity of 455.65 mA h g^(-1) at an elevated temperature of 525℃.The discharge specific capacity of the thermal cell at 500 mA amounts to 63%of that at 100 mA,showcasing exceptional high-current discharging performance.When assembled as prototypes with fourteen single cells connected in series,the thermal batteries deliver an activation time of 38 ms and a discharge time of 32 s with the current density of 100 mA cm^(-2).These findings suggest that Ga,Ba co-doped LLZO solid-state electrolytes with high ionic conductivities holds great potential for high-capacity,quick-initiating and high-current discharging thermal batteries.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
All-solid-state batteries(ASSBs)have garnered significant interest as the next-generation in battery technology,praised for their superior safety and high energy density.However,a conductive agent accelerates the unde...All-solid-state batteries(ASSBs)have garnered significant interest as the next-generation in battery technology,praised for their superior safety and high energy density.However,a conductive agent accelerates the undesirable side reactions of sulfide-based solid electrolytes(SEs),resulting in poor electrochemical properties with increased interfacial resistance.Here,we propose a wet chemical method rationally designed to achieve a conformal coating of lithium-indium chloride(Li_(3)InCl_(6))onto vapor-grown carbon fibers(VGCFs)as conductive agents.First,with the advantage of the Li_(3)InCl_(6) protective layer,use of VGCF@Li_(3)InCl_(6) leads to enhanced interfacial stability and improved electrochemical properties,including stable cycle performance.These results indicate that the Li_(3)InCl_(6) protective layer suppresses the unwanted reaction between Li_(6)PS_(5)Cl(LPSCl)and VGCF.Second,VGCF@Li_(3)InCl_(6) effectively promotes polytetrafluoroethylene(PTFE)fibrillization,leading to a homogeneous electrode microstructure.The uniform distribution of the cathode active material(CAM)in the electrode results in reduced charge-transfer resistance(R_(ct))and enhanced Li-ion kinetics.As a result,a full cell with the LiNi_(x)Mn_(y)Co_(z)O_(2)(NCM)/VGCF@Li_(3)InCl_(6) electrode shows an areal capacity of 7.7mAhcm^(−2) at 0.05 C and long-term cycle stability of 77.9%over 400 cycles at 0.2 C.This study offers a strategy for utilizing stable carbon-based conductive agents in sulfide-based ASSBs to enhance their electrochemical performance.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
The performance of lithium metal batteries(LMBs)is greatly hampered by the unstable solid electrolyte interphase(SEI)and uncontrollable growth of Li dendrites.To address this question,we developed a weak polar additiv...The performance of lithium metal batteries(LMBs)is greatly hampered by the unstable solid electrolyte interphase(SEI)and uncontrollable growth of Li dendrites.To address this question,we developed a weak polar additive strategy to develop stable and dendrite-free electrolyte for LMBs.In this paper,the effects of additives on the Li^(+)solvation kinetics and the electrode-electrolyte interphases(EEI)formation are discussed.The function of synergistically boosting the superior Li^(+)kinetics and alleviating solvent decomposition on the electrodes is confirmed.From the thermodynamic view,the exothermic process of defluorination reaction for 3,5-difluoropyridine(3,5-DFPy)results in the formation of LiF-rich SEI layer for promoting the uniform Li nucleation and deposition.From the dynamic view,the weakened Li^(+)solvation structure induced by weak polar 3,5-DFPy contributes to better Li^(+)kinetics through the easier Li^(+)desolvation.As expected,Li||Li cell with 1.0 wt%3,5-DFPy exhibits 400 cycles at 1.0 mA cm^(-2)with a deposition capacity of 0.5 mAh cm^(-2),and the Li||LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)batteries delivers the highly reversible capacity after 200 cycles.展开更多
Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage c...Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials.In this study,we present the development and synthesis of a 0.6Li_(2)S-ZrCl_(4)solid electrolyte,demonstrating an ion conductivity of 1.9×10^(–3)S/cm at 25°C.Under a pressure of 500 MPa,the relative density of the electrolyte can reach 97.37%,showcasing its commendable compressibility.0.6Li_(2)S-ZrCl_(4)served as the electrolyte,and we assembled batteries utilizing a LiCoO_(2)(LCO)positive electrode,Li_(9.54)Si_(1.74)P_(1.44)S_(11.7)Cl_(0.3)(LSPSCl)coating,and Li-In negative electrode for laboratory testing.At 25°C,this all-solid-state battery demonstrated an impressive discharge capacity retention rate of86.99%(with a final discharge specific capacity of 110.5 m Ah/g)after 250 cycles at 24 m A/g and 100 MPa stack pressure.Upon substituting the positive electrode material with LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)and assembling an all-solid-state battery,it demonstrated a discharge capacity retention rate of 74.17%after200 cycles at 3.6 m A/g and 100 MPa stack pressure in an environment at 25°C(with a final discharge specific capacity of 103.3 m A/g).Our findings hold significant implications for the design of novel superionic conductors,thereby contributing to the advancement of all-solid-state battery technology.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(Grant No.22075064,52302234,52272241)Zhejiang Provincial Natural Science Foundation of China under Grant No.LR24E020001+2 种基金Natural Science of Heilongjiang Province(No.LH2023B009)China Postdoctoral Science Foundation(2022M710950)Heilongjiang Postdoctoral Fund(LBH-Z21131),National Key Laboratory Projects(No.SYSKT20230056).
文摘To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.
基金supported by the National Natural Science Foundation of China(Nos.52172243,52371215)。
文摘All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.
基金the Natural Sci-ence Foundation of Shandong Province(Nos.ZR2022QE014,ZR2021QH237)the Guangdong Provincial Key Laboratory of Elec-tronic Functional Materials and Devices(No.EFMD2022017M)+1 种基金the National Natural Science Foundation of China(Grant Nos.52401221,51971120,U1902221)the Medical StaffScience and Technology Plan of Shandong Province(No.SDYWZGKCJH2022073).
文摘Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature.However,the use of Succinonitrile is limited due to its corrosion of Li metal.Herein,we report a solid polymer electrolyte with high ionic conductivity(2.17×10^(−3)S cm^(−1),35°C)enhanced by Ti_(3)C_(2)T_(x).Corrosion of the Li anode is prevented due to the Succinonitrile molecules being efficiently anchored by Ti_(3)C_(2)T_(x).Meanwhile,the coordination environment of Li^(+)is weakened due to the introduction of competitive coordination induction effects into the polymer electrolyte,resulting in efficient Li^(+)conduction.Furthermore,the mechanical properties of the electrolyte are enhanced by modulating the ratio of Ti_(3)C_(2)T_(x)to suppress the growth of Li dendrites.Therefore,Li||Li symmetric batteries deliver stable cycling up to 8000 h at 28°C.LiFePO4||Li full batteries exhibit excellent cycling stability of 151.7 mAh g^(−1)with a capacity retention of 99.3%after 300 cycles.This work not only presents a new idea to suppress the corrosion of the Li anode by Succinonitrile but also provides a simple,feasible,and scalable strategy for high-performance Li metal batteries.
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 a National Research Foundation of Korea(NRF)Grant funded by the Ministry of Science and ICT(2021R1A2C1014294,2022R1A2C3003319)the BK21 FOUR(Fostering Outstanding Universities for Research)through the National Research Foundation(NRF)of Korea.
文摘A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.
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supported by the Natural Science Foundation of China(52488201)。
文摘Quasi-solid-state lithium-metal batteries(QSLMBs)are promising candidates for next-generation battery systems due to their high energy density and enhanced safety.However,their practical application has been hindered by low ionic conductivity and the growth of lithium dendrites.To achieve ordered transport of Li^(+)ions in quasi-solid electrolytes(QSEs),improve ionic conductivity,and homogenize Li^(+)fluxes on the surface of the lithium metal anode(LMA),we propose a novel method.This method involves constructing"ion relay stations"in QSEs by introducing cyano-functionalized boron nitride nanosheets into pentaerythritol tetraacrylate(PETEA)-based polymer electrolytes.The functionalized boron nitride nanosheets promote the dissociation of lithium salts through ion-dipole interactions,optimizing the solvated structure to facilitate the orderly transport of Li+ions,resulting in an ionic conductivity of2.5×10^(-3)S cm^(-1)at 30℃.Notably,this strategy regulates the Li^(+)distribution on the surface of the LMA,effectively inhibiting the growth of lithium dendrites,Li‖Li symmetrical cells using this type of electrolyte maintain stability for over 2000 h at 2 mA cm^(-2)and 2 mAh cm^(-2).Additionally,with a high LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)loading of 8.5 mg cm^(-2),the cells exhibit excellent cycling performance,retaining a high capacity after 400 cycles.This innovative QSE design strategy represents a significant advancement towards the development of high-performance QSLMBs.
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.
基金supported by the National Research Foundation of Korea(NRF)(no.:NRF-2020M3H4A3081874)the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(no.:GTL24011-000)the Korea Research Institute of Chemical Technology(KRICT),Republic of Korea(no.KS2422-20).
文摘Solid polymer electrolytes have garnered significant attention for lithium batteries because of their flexibility and safety.However,poor ionic conductivity,lithium dendrite formation,and high impedance hinder their practical application.In this study,a thin,flexible,3D hybrid solid electrolyte(3DHSE)is prepared by in situ thermal cross-linking polymerization with electrospun 3D nanowebs.The 3DHSE comprises Al-doped Li_(7)La_(3)Zr_(2)O_(12)(ALLZO)embedded in electrospun poly(vinylidene fluoride-cohexafluoropropylene)(PVDF-HFP)nonwoven 3D nanowebs and an in situ cross-linked polyethylene oxide(PEO)-based solid polymer electrolyte.The 3DHSE exhibits high tensile strength(6.55 MPa),a strain of 40.28%,enhanced ionic conductivity(7.86×10^(-4) S cm^(-1)),and a superior lithium-ion transference number(0.76)to that of the PVDF-HFP-based solid polymer electrolyte(PSPE).This enables highly stable lithium plating/stripping cycling for over 900 h at 25℃ with a current density of 0.2 mA cm^(-2).The LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NCM811)/3DHSE/Li cell has a higher capacity(140.56 mAh g^(-1) at 0.1 C)than the NCM811/PSPE/Li cell(124.88 mAh g^(-1) at 0.1 C)at 25℃.The 3DHSE enhances mechanical properties,stabilizes interfacial contact,improves ion transport,prevents NCM811 cracking,and significantly boosts cycling performance.This study highlights the potential of the 3DHSE as a candidate for advanced lithium polymer battery technology.
基金supported by the Basic Science Research Program through National Research Foundation of Korea(NRF)grant funded by the Ministry of Science and ICT(RS-2022-NR070534)supported by the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(2710024139)。
文摘Li-argyrodites are promising solid electrolytes(SEs)for solid-state Li-ion batteries(SSLBs),but their large-scale industrial application remains a challenge.Conventional synthesis methods for SEs suffer from long reaction times and high energy consumption.In this study,we present a wet process for the synthesis of halogen-rich argyrodite Li_(6-a)PS_(5-a)Cl_(1+a)precursors(LPSCl_(1+a)-P,a=0–0.7)via an energysaving microwave-assisted process.Utilizing vibrational heating,we accelerate the formation of Liargyrodite precursor,even at excessive Cl-ion concentration,which significantly shortens the reaction time compared to traditional methods.After crystallization,we successfully synthesize the Liargyrodite,Li_(5.5)PS_(4.5)Cl_(1.5),which exhibits the superior ionic conductivity(7.8 mS cm^(-1))and low activation energy(0.23 eV)along with extremely low electric conductivity.The Li_(5.5)PS_(4.5)Cl_(1.5)exhibits superior Li compatibility owing to its high reversible striping/plating ability(over 5000 h)and high current density acceptability(1.3 mA cm^(-2)).It also exhibits excellent cycle reversibility and rate capability with NCM622 cathode(148.3 mA h g^(-1)at 1 C for 100 cycles with capacity retention of 85.6%).This finding suggests a potentially simpler and more scalable synthetic route to produce high-performance SEs.
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].
基金support from Generalitat Valenciana under Pla Complementari“Programa de Materials Avanc¸ats”,2022(grant number MFA/2022/030)Ministerio de Ciencia,Innovaci´on y Universidades(Spain)(grant number MCIN/AEI/10.13039/501100011033)+1 种基金support from UJI(UJI-2023-16 and GACUJIMC/2023/08)Generalitat Valenciana through FPI Fellowship Program(grant numbers ACIF/2020/294 and CIACIF/2021/050).
文摘This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Process(CSP).By optimizing the sintering pressure,it is achieved an intimate contact between the cathode and the solid electrolyte,leading to an enhanced electrochemical performance.Bilayers cold sintered at 300 MPa and a low-sintering temperature of 150℃exhibit high ionic conductivities(0.5 mS cm^(-1))and stable specific capacities at room temperature(160.1 mAh g^(-1)LFP at C/10 and 75.8 mAh g^(-1)_(LFP)at 1 C).Moreover,an operando electrochemical impedance spectroscopy(EIS)technique is employed to identify limiting factors of the bilayer kinetics and to anticipate the overall electrochemical behavior.Results suggest that capacity fading can occur in samples prepared with high sintering pressures due to a volume reduction in the LFP crystalline cell.This work demonstrates the potential of CSP to produce straightforward high-performance bilayers and introduces a valuable non-destructive instrument for understanding and avoiding degradation in solid-state lithium-based batteries.
基金supported by the National Natural Science Foundation of China(No.52472137)the Talent Introduction Research Project of Hebei University(No.521100224231)the Shanghai Magnolia Talent Plan Pujiang Project(23PJ1415600)。
文摘Compared to traditional liquid electrolyte batteries,solid metal batteries offer advantages such as a wide operating temperature range,high energy density,and improved safety,making them a promising energy storage technology.Solid electrolytes,as the core components of solid‐state batteries,are key factors in advancing solid‐state battery technology.Among various solid electrolytes,Na super ionic conductor(NASICON)‐type solid electrolytes exhibit high ionic conductivity(10−3 S·cm−1),a wide electrochemical window,and good thermal stability,providing room for the development of high energy‐density solid metal batteries.Since the discovery of NASICON‐type solid electrolytes in 1976,interest in their use in all‐solid‐state battery development has grown significantly.In this review,we comprehensively analyze the common features of NASICON lithium‐ion conductors and NASICON sodium‐ion conductors,review the historical development of NASICON‐type solid electrolytes,systematically summarize the transport mechanisms of metal cations in NASICON‐type solid electrolytes,discuss the latest strategies for enhancing ionic conductivity,elaborate on the latest methods for improving mechanical stability and interface stability,and point out the requirements of high energy density devices for NASICON‐type solid electrolytes as well as three types of in situ characterization techniques for interfaces.Finally,we highlight the challenges and potential solutions for the future development of NASICON‐type solid electrolytes and solid‐state metal batteries.
基金the National Key R&D Program of China(No.2023YFC3009501)the National Natural Science Foundation of China(No.52374298)+1 种基金the project of State Key Laboratory of Explosion Science and Safety Protection(Beijing Institute of Technology,No.QNKT23-17)Aeronautical Science Foundation of China(No.20174072003).
文摘Garnet Li_(7)La_(3)Zr_(2)O_(12)(LLZO)electrolytes have been recognized as a promising candidate to replace liquid/molten-state electrolytes in battery applications due to their exceptional performance,particularly Ga-doped LLZO(LLZGO),which exhibits high ionic conductivity.However,the limited size of the Liþtransport bottleneck restricts its high-current discharging performance.The present study focuses on the synthesis of Ga^(3+)þand Ba^(2+)þco-doped LLZO(LLZGBO)and investigates the influence of doping contents on the morphology,crystal structure,Liþtransport bottleneck size,and ionic conductivity.In particular,Ga_(0.32)Ba_(0.15)exhibits the highest ionic conductivity(6.11E-2 S cm^(-1) at 550 C)in comparison with other compositions,which can be attributed to its higher-energy morphology,larger bottleneck and unique Liþtransport channel.In addition to Ba^(2+),Sr^(2+)þand Ca^(2+)have been co-doped with Ga3þinto LLZO,respectively,to study the effect of doping ion radius on crystal structures and the properties of electrolytes.The characterization results demonstrate that the easier Liþtransport and higher ionic conductivity can be obtained when the electrolyte is doped with larger-radius ions.As a result,the assembled thermal battery with Ga_(0.32)Ba_(0.15)-LLZO electrolyte exhibits a remarkable voltage platform of 1.81 V and a high specific capacity of 455.65 mA h g^(-1) at an elevated temperature of 525℃.The discharge specific capacity of the thermal cell at 500 mA amounts to 63%of that at 100 mA,showcasing exceptional high-current discharging performance.When assembled as prototypes with fourteen single cells connected in series,the thermal batteries deliver an activation time of 38 ms and a discharge time of 32 s with the current density of 100 mA cm^(-2).These findings suggest that Ga,Ba co-doped LLZO solid-state electrolytes with high ionic conductivities holds great potential for high-capacity,quick-initiating and high-current discharging thermal batteries.
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supported by the Korea Institute for Advancement of Technology(KIAT)grant funded by the Korean Government(MOTIE)(RS-2024-00417730,HRD Program for Industrial Innovation)supported by the Technology Innovation Program(or Industrial Strategic Technology Development Program-Materials&Components Technology Development Program)(20024261),Development of thick film electrodes and cell manufacturing technology for a high-performance lithium iron phosphate battery with energy density of over 200 Wh/kg was funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea).
文摘All-solid-state batteries(ASSBs)have garnered significant interest as the next-generation in battery technology,praised for their superior safety and high energy density.However,a conductive agent accelerates the undesirable side reactions of sulfide-based solid electrolytes(SEs),resulting in poor electrochemical properties with increased interfacial resistance.Here,we propose a wet chemical method rationally designed to achieve a conformal coating of lithium-indium chloride(Li_(3)InCl_(6))onto vapor-grown carbon fibers(VGCFs)as conductive agents.First,with the advantage of the Li_(3)InCl_(6) protective layer,use of VGCF@Li_(3)InCl_(6) leads to enhanced interfacial stability and improved electrochemical properties,including stable cycle performance.These results indicate that the Li_(3)InCl_(6) protective layer suppresses the unwanted reaction between Li_(6)PS_(5)Cl(LPSCl)and VGCF.Second,VGCF@Li_(3)InCl_(6) effectively promotes polytetrafluoroethylene(PTFE)fibrillization,leading to a homogeneous electrode microstructure.The uniform distribution of the cathode active material(CAM)in the electrode results in reduced charge-transfer resistance(R_(ct))and enhanced Li-ion kinetics.As a result,a full cell with the LiNi_(x)Mn_(y)Co_(z)O_(2)(NCM)/VGCF@Li_(3)InCl_(6) electrode shows an areal capacity of 7.7mAhcm^(−2) at 0.05 C and long-term cycle stability of 77.9%over 400 cycles at 0.2 C.This study offers a strategy for utilizing stable carbon-based conductive agents in sulfide-based ASSBs to enhance their electrochemical performance.
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supported by the National Natural Science Foundation of China(U21A20311)Researchers Supporting Project Number(RSP2025R304),King Saud University,Riyadh,Saudi Arabia。
文摘The performance of lithium metal batteries(LMBs)is greatly hampered by the unstable solid electrolyte interphase(SEI)and uncontrollable growth of Li dendrites.To address this question,we developed a weak polar additive strategy to develop stable and dendrite-free electrolyte for LMBs.In this paper,the effects of additives on the Li^(+)solvation kinetics and the electrode-electrolyte interphases(EEI)formation are discussed.The function of synergistically boosting the superior Li^(+)kinetics and alleviating solvent decomposition on the electrodes is confirmed.From the thermodynamic view,the exothermic process of defluorination reaction for 3,5-difluoropyridine(3,5-DFPy)results in the formation of LiF-rich SEI layer for promoting the uniform Li nucleation and deposition.From the dynamic view,the weakened Li^(+)solvation structure induced by weak polar 3,5-DFPy contributes to better Li^(+)kinetics through the easier Li^(+)desolvation.As expected,Li||Li cell with 1.0 wt%3,5-DFPy exhibits 400 cycles at 1.0 mA cm^(-2)with a deposition capacity of 0.5 mAh cm^(-2),and the Li||LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)batteries delivers the highly reversible capacity after 200 cycles.
基金financially supported by Natural Science Foundation of Hebei Province(Nos.B2020203037,F2021203097)Science Research Project of Hebei Education Department(No.JZX2024022)National Natural Science Foundation of China(Nos.52022088,51971245)。
文摘Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials.In this study,we present the development and synthesis of a 0.6Li_(2)S-ZrCl_(4)solid electrolyte,demonstrating an ion conductivity of 1.9×10^(–3)S/cm at 25°C.Under a pressure of 500 MPa,the relative density of the electrolyte can reach 97.37%,showcasing its commendable compressibility.0.6Li_(2)S-ZrCl_(4)served as the electrolyte,and we assembled batteries utilizing a LiCoO_(2)(LCO)positive electrode,Li_(9.54)Si_(1.74)P_(1.44)S_(11.7)Cl_(0.3)(LSPSCl)coating,and Li-In negative electrode for laboratory testing.At 25°C,this all-solid-state battery demonstrated an impressive discharge capacity retention rate of86.99%(with a final discharge specific capacity of 110.5 m Ah/g)after 250 cycles at 24 m A/g and 100 MPa stack pressure.Upon substituting the positive electrode material with LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)and assembling an all-solid-state battery,it demonstrated a discharge capacity retention rate of 74.17%after200 cycles at 3.6 m A/g and 100 MPa stack pressure in an environment at 25°C(with a final discharge specific capacity of 103.3 m A/g).Our findings hold significant implications for the design of novel superionic conductors,thereby contributing to the advancement of all-solid-state battery technology.
