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
Nasicon materials （sodium superionic conductors） such as Li1.5A10.5Ge1.5（PO4）3 （LAGP） and Li1.4Al0.4Til.6（PO4）3 （LATP） have been considered as important solid electrolytes due to their high ionic conductivit...Nasicon materials （sodium superionic conductors） such as Li1.5A10.5Ge1.5（PO4）3 （LAGP） and Li1.4Al0.4Til.6（PO4）3 （LATP） have been considered as important solid electrolytes due to their high ionic conductivity and chemical stability. Compared to LAGP, LATP has higher bulk conductivity around 10^-3 S/cm at room temperature; however, the apparent grain boundary conductivity is almost two orders of magnitude lower than the bulk, while LAGP has similar bulk and grain boundary conductivity around the order of 10-4 S/cm. To make full use of the advantages of the two electrolytes, pure phase Li1.5A10.5Ge1.5（PO4）3 and Li1.4A10.4Ti1.6（PO4）3 were synthesized through solid state reaction, a series of composite electrolytes consisting of LAGP and LATP with different weight ratios were designed. XRD and variable temperature AC impedance spectra were carried out to clarify the crystal structure and the ion transport properties of the composite electrolytes. The results indicate that the composite electrolyte with the LATP/LAGP weight ratio of 80：20 achieved the highest bulk conductivity which shall be due to the formation of solid solution phase Li1.42Alo.42Geo.3Ti1 .28（PO4）3, while the highest grain boundary conductivity appeared at the LATP/LAGP weight ratio of 20：80 which may be due to the excellent interfacial phase between Li1＋xAlxGeyTi2-x-y（PO4）3/LATE All the composite electrolytes demonstrated higher total conductivity than the pure LAGP and LATE which highlights the importance of heterogeneous interface on regulating the ion transport properties.展开更多
The composite quasi solid state electrolytes（CQSE） is firstly synthesized with quasi solid state electrolytes（QSE） and lithium-ion-conducting material Li1.4Al0.4Ti1.6（PO4）3（LATP）, and the QSE consists of [LiG4...The composite quasi solid state electrolytes（CQSE） is firstly synthesized with quasi solid state electrolytes（QSE） and lithium-ion-conducting material Li1.4Al0.4Ti1.6（PO4）3（LATP）, and the QSE consists of [LiG4][TFSI] with fumed silica nanoparticles. Compared with LATP, CQSE greatly improves the interface conductance of solid electrolytes. In addition,it has lower liquid volume relative to QSE. Although the liquid volume fraction of CQSE is droped to 60%, its conductivity can also reach 1.39 × 10^-4S/cm at 20℃. Linear sweep voltammetry（LSV） is conducted on each composite electrolyte.The results show the possibility that CQSE has superior electrochemical stability up to 5.0 V versus Li/Li^＋1. TG curves also show that composite electrolytes have higher thermal stability. In addition, the performance of Li/QSE/Li Mn2O4 and Li/CQSE/Li Mn2O4 batteries is evaluated and shows good electrochemical characteristics at 60℃.展开更多
Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. Ho...Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fiuorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital(LUMO), which leads to significant consumption of the fiuorinated components upon cycling.Herein, attenuating reductive decomposition of fiuorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate(VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fiuoroethylene carbonate(FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fiuorinated electrolytes in high-voltage Li-metal batteries.展开更多
1.Introduction.The ever-increasing demands for high-energy-density power supply systems have driven the rapid development of conventional lithium-ion batteries,of which properties are approaching to the ceiling.In the...1.Introduction.The ever-increasing demands for high-energy-density power supply systems have driven the rapid development of conventional lithium-ion batteries,of which properties are approaching to the ceiling.In the meantime,the safety of lithium-ion batteries also grabs more attention as their wide application in consumer electronics and electric vehicles.The safety of battery system can be enhanced inherently by replacing the flammable liquid electrolytes with inorganic solid electrolytes,which makes solid-state battery one of the most promising candidates of next-generation energy storage systems[1-3].Additionally,the improvements in energy density are foreseen as solid electrolytes enable lithium metal anode[4-11]and high-voltage cathodes[12-15].展开更多
The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious int...The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.展开更多
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
Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interf...Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of sodium-potassium(NaK)alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the physical contact of the electrode-electrolyte interface.Additionally,the filling of SiO_(2) nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 hrs.The full cell coupled with Na_(3)V_(2)(PO_(4))_(2) cathodes had an initial discharge capacity of 106.8 mAh·g^(-1) with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1) even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.展开更多
The 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
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
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
FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium stor...FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium storage.Rational structural design is one way to overcome these drawbacks.In this work,MIL-88B-Fe-derived FeS_(2)nanoparticles/N-doped carbon nanofibers(M-FeS_(2)@CNFs)with expansion buffer capability are designed and synthesized for high-performance PIB anodes via electrospinning and subsequent sulfurization.The uniformly distributed cavity-type porous structure effectively mitigates the severe aggregation problem of FeS_(2)nanoparticles during cycling and buffers the volume change,further enhancing the potassium storage capacity.Meanwhile,the robust KF-rich solid electrolyte interphase induced by methyl trifluoroethylene carbonate(FEMC)additive improves the cycling stability of the M-FeS_(2)@CNF anode.In the electrolyte with 3 wt%FEMC,the M-FeS_(2)@CNF anode shows a reversible specific capacity of 592.7 mA h g^(-1)at 0.1 A g^(-1),an excellent rate capability of 327.1 mA h g^(-1)at 5 A g^(-1),and a retention rate 80.7%over 1000 cycles at 1 A g^(-1).More importantly,when assembled with a K_(1.84)Ni[Fe(CN)_(6)]_(0.88)·0.49H_(2)O cathode,the full battery manifests excellent cycle stability and high rate performance.This study demonstrates the significant importance of the synergistic effect of structural regulation and electrolyte optimization in achieving high cycling stability of PIBs.展开更多
The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated...The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.展开更多
Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) ...Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) with weak solvation structures is established by the multi-anion strategy.Multiple anions in the electrolyte strengthen the anion-solvent interactions through stronger ion–dipole interactions.This reduces the quantity of free solvent and improves the reduction resistance of solvents.In addition,the Li ion–solvent interaction is weakened,facilitating the anions to enter the solvation sheaths of Li ions.This multi-anion-dominated weak solvation structures boost Li ion diffusion in the electrolyte,accelerate the desolvation process of Li ions,and induce inorganic-rich solid electrolyte interphase and uniform Li deposition.An average Coulombic efficiency of 99.1%for repeated Li plating/stripping can be achieved.Li||LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cells with a high cathode loading of 3.0 m A h cm^(-2) can maintain a capacity retention as high as 95% after 150 cycles.This finding provides novel standpoints to modulate the interaction of solvation structures and extend the lifespan of high-energy–density Li metal batteries.展开更多
Single ion gel polymer electrolyte has the advantages of high Li^(+)conductivity and dendrite mitigation.However,the addition of organic solvent makes the electrolyte flammable,posing serious safety hazards.Herein,we ...Single ion gel polymer electrolyte has the advantages of high Li^(+)conductivity and dendrite mitigation.However,the addition of organic solvent makes the electrolyte flammable,posing serious safety hazards.Herein,we report a flame-retard ant cross-linked sp^(3)boron-based single-ion gel polymer electrolyte(BSIPE).BSIPE was prepared by a simple one-step photoinitiated in situ thiol-ene click reaction.Due to the boron-based anions being immobilized in the cross-linking network,the developed BSIPE/PFN exhibits a high t_(Li^(+))(0.87),which can mitigate concentration polarization phenomenon and suppress the growth of lithium dendrites.BSIPE/PFN plasticized with triethyl phosphate(TEP),fluoroethylene carbonate(FEC)and LiNO_(3)exhibits enhanced ionic conductivity of 4.25×10^(-4)S cm^(-1)at 30℃ and flame retardancy.FEC and LiNO_(3) are conducive to form a stable solid electrolyte interphase(SEI)rich in Li_(3)N and LiF to improve interface stability.As expected,the dendrite-free Li‖BSIPE/PFN‖Li symmetric cell exhibits considerable cycling life over 1500 h.BSIPE/PFN significantly boosts the performance of LFP‖Li cell,which displays a capacity retention of 84.6%after 500 cycles.The BSIPE/PFN has promising applications in highsafety and high-performance lithium metal batteries.展开更多
Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a th...Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles,which seriously limits the actual energy density of sulfide all-solid-state lithium batteries(ASSLBs).Fortunately,the preparation of sulfide-polymer composite solid electrolyte(SPCSE)membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties.In this review,recent progress of SPCSE membranes for ASSLBs is summarized.The classification of components in SPCSE membranes is first introduced briefly.Then,the preparation methods of SPCSE membranes are categorized according to process characteristics,in which the challenges of different methods and their corresponding solutions are carefully reviewed.The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance.Finally,we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.展开更多
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
The growth of dendrites and the side reactions occurring at the Zn anode pose significant challenges to the commercialization of aqueous Zn-ion batteries(AZIBs). These challenges arise from the inherent conflict betwe...The growth of dendrites and the side reactions occurring at the Zn anode pose significant challenges to the commercialization of aqueous Zn-ion batteries(AZIBs). These challenges arise from the inherent conflict between mass transfer and electrochemical kinetics. In this study, we propose the use of a multifunctional electrolyte additive based on the xylose(Xylo) molecule to address these issues by modulating the solvation structure and electrode/electrolyte interface, thereby stabilizing the Zn anode. The introduction of the additive alters the solvation structure, creating steric hindrance that impedes charge transfer and then reduces electrochemical kinetics. Furthermore, in-situ analyses demonstrate that the reconstructed electrode/electrolyte interface facilitates stable and rapid Zn^(2+)ion migration and suppresses corrosion and hydrogen evolution reactions. As a result, symmetric cells incorporating the Xylo additive exhibit significantly enhanced reversibility during the Zn plating/stripping process, with an impressively long lifespan of up to 1986 h, compared to cells using pure ZnSO4electrolyte. When combined with a polyaniline cathode, the full cells demonstrate improved capacity and long-term cyclic stability. This work offers an effective direction for improving the stability of Zn anode via electrolyte design, as well as highperformance AZIBs.展开更多
Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic react...Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic reactions in zinc perchlorate electrolytes,which is caused by the fast corrosive kinetics at room temperature.Herein,a concentrated perchlorate-based electrolyte consisting of 4.0 M Zn(ClO_(4))_(2)and saturated NaClO_(4)solution is developed to achieve dendrite-free and stable AZIBs at room temperature.The ClO_(4)−participates in the primary solvation sheath of Zn^(2+),facilitating the in situ formation of Zn_(5)(OH)_(8)Cl_(2)·H_(2)O-rich solid electrolyte interphase(SEI)to suppress the corrosion effect of ClO_(4)^(−).The Zn anode protected by the SEI achieves stable Zn plating/stripping over 3000 h.Furthermore,the MnO_(2)||Zn full cells manifest a stable specific capacity of 200 mAh·g^(−1)at 28℃and 101 mAh·g^(−1)at−20℃.This work introduces a promising approach for boosting the room-temperature performance of perchlorate-based electrolytes for AZIBs.展开更多
Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a s...Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a stable solid electrolyte interphase(SEI)layer is a great challenge for QSPE-based lithium(Li)metal batteries(LMBs).Herein,unlike previously reports that the reconstruction of Li^(+)solvation structures in QSPE requires time-consuming bottom-up polymer synthesis,in current study,a facile approach has been developed to reconstruct the Li^(+)solvation structures in QSPE by adjustment of the salt concentrations.The high proportion of Li^(+)-anion complexes can effectively accelerate interfacial Li^(+)diffusion,mitigate the decompositions of organic solvents and induce the formation of a LiF-rich SEI layer,contributing to suppressed Li-dendrite growth.As a result,the Li/QSPE-3/LiFePO_(4)(LFP)cell performs an ultralong lifespan with capacity retention of 77.4%over 3000 cycles at 1 C.With a high-voltage LiCoO_(2)cathode,the cell can stably cycle over 200 cycles at 25℃(capacity retention of∼83.8%).With accelerated ion transport dynamics due to the reconstructed Li^(+)solvation structure,the QSPE-3(the salt concentration is 3 M)is applicable in a wide temperature range.The Li/QSPE-3/LFP full cell exhibits 58.1%and 102.6%of discharge capacity at−15 and 90℃,respectively,compared to those operated at 25℃This study demonstrates a facile yet effective approach on enhancing electrode/electrolyte interfacial stability,enabling the LMBs with simultaneously enhanced safety and high energy density.展开更多
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Project supported by the National Key Research and Development Program of China(Grant No.2016YFB0100100)the National Natural Science Foundation of China(Grant Nos.52315206 and 51502334)Fund from Beijing Municipal Science&Technology Commission,China(Grant No.D171100005517001)
文摘Nasicon materials （sodium superionic conductors） such as Li1.5A10.5Ge1.5（PO4）3 （LAGP） and Li1.4Al0.4Til.6（PO4）3 （LATP） have been considered as important solid electrolytes due to their high ionic conductivity and chemical stability. Compared to LAGP, LATP has higher bulk conductivity around 10^-3 S/cm at room temperature; however, the apparent grain boundary conductivity is almost two orders of magnitude lower than the bulk, while LAGP has similar bulk and grain boundary conductivity around the order of 10-4 S/cm. To make full use of the advantages of the two electrolytes, pure phase Li1.5A10.5Ge1.5（PO4）3 and Li1.4A10.4Ti1.6（PO4）3 were synthesized through solid state reaction, a series of composite electrolytes consisting of LAGP and LATP with different weight ratios were designed. XRD and variable temperature AC impedance spectra were carried out to clarify the crystal structure and the ion transport properties of the composite electrolytes. The results indicate that the composite electrolyte with the LATP/LAGP weight ratio of 80：20 achieved the highest bulk conductivity which shall be due to the formation of solid solution phase Li1.42Alo.42Geo.3Ti1 .28（PO4）3, while the highest grain boundary conductivity appeared at the LATP/LAGP weight ratio of 20：80 which may be due to the excellent interfacial phase between Li1＋xAlxGeyTi2-x-y（PO4）3/LATE All the composite electrolytes demonstrated higher total conductivity than the pure LAGP and LATE which highlights the importance of heterogeneous interface on regulating the ion transport properties.
基金supported by the National Natural Science Foundation of China(Grant Nos.52315206 and 51502334)the Funds from the Ministry of Science and Technology of China(Grant No.2016YFB0100100)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA09010000)the Foundation from Beijing Municipal Science&Technology Commission(Grant No.D171100005517001)
文摘The composite quasi solid state electrolytes（CQSE） is firstly synthesized with quasi solid state electrolytes（QSE） and lithium-ion-conducting material Li1.4Al0.4Ti1.6（PO4）3（LATP）, and the QSE consists of [LiG4][TFSI] with fumed silica nanoparticles. Compared with LATP, CQSE greatly improves the interface conductance of solid electrolytes. In addition,it has lower liquid volume relative to QSE. Although the liquid volume fraction of CQSE is droped to 60%, its conductivity can also reach 1.39 × 10^-4S/cm at 20℃. Linear sweep voltammetry（LSV） is conducted on each composite electrolyte.The results show the possibility that CQSE has superior electrochemical stability up to 5.0 V versus Li/Li^＋1. TG curves also show that composite electrolytes have higher thermal stability. In addition, the performance of Li/QSE/Li Mn2O4 and Li/CQSE/Li Mn2O4 batteries is evaluated and shows good electrochemical characteristics at 60℃.
基金supported by the National Natural Science Foundation of China (Nos. 22379121, 62005216)Basic Public Welfare Research Program of Zhejiang (No. LQ22F050013)+1 种基金Zhejiang Province Key Laboratory of Flexible Electronics Open Fund (2023FE005)Shenzhen Foundation Research Program (No. JCYJ20220530112812028)。
文摘Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fiuorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital(LUMO), which leads to significant consumption of the fiuorinated components upon cycling.Herein, attenuating reductive decomposition of fiuorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate(VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fiuoroethylene carbonate(FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fiuorinated electrolytes in high-voltage Li-metal batteries.
文摘1.Introduction.The ever-increasing demands for high-energy-density power supply systems have driven the rapid development of conventional lithium-ion batteries,of which properties are approaching to the ceiling.In the meantime,the safety of lithium-ion batteries also grabs more attention as their wide application in consumer electronics and electric vehicles.The safety of battery system can be enhanced inherently by replacing the flammable liquid electrolytes with inorganic solid electrolytes,which makes solid-state battery one of the most promising candidates of next-generation energy storage systems[1-3].Additionally,the improvements in energy density are foreseen as solid electrolytes enable lithium metal anode[4-11]and high-voltage cathodes[12-15].
基金supported by the National Natural Science Foundation of China(Nos.52172214,52272221,52171182)the Postdoctoral Innovation Project of Shandong Province(No.202102003)+2 种基金The Key Research and Development Program of Shandong Province(2021ZLGX01)the Qilu Young Scholar ProgramHPC Cloud Platform of Shandong University are also thanked.
文摘The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.
基金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National Natural Science Foundation of China (52073253)。
文摘Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of sodium-potassium(NaK)alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the physical contact of the electrode-electrolyte interface.Additionally,the filling of SiO_(2) nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 hrs.The full cell coupled with Na_(3)V_(2)(PO_(4))_(2) cathodes had an initial discharge capacity of 106.8 mAh·g^(-1) with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1) even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.
基金supported by 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(22179063,22479078,and 22409093)the Natural Science Foundation of Jiangsu Province of China(BK20240579)。
文摘FeS_(2)is a promising anode material for potassium-ion batteries(PIBs),with the advantages of low cost and high capacity.However,it still faces challenges of capacity fading and poor rate performance in potassium storage.Rational structural design is one way to overcome these drawbacks.In this work,MIL-88B-Fe-derived FeS_(2)nanoparticles/N-doped carbon nanofibers(M-FeS_(2)@CNFs)with expansion buffer capability are designed and synthesized for high-performance PIB anodes via electrospinning and subsequent sulfurization.The uniformly distributed cavity-type porous structure effectively mitigates the severe aggregation problem of FeS_(2)nanoparticles during cycling and buffers the volume change,further enhancing the potassium storage capacity.Meanwhile,the robust KF-rich solid electrolyte interphase induced by methyl trifluoroethylene carbonate(FEMC)additive improves the cycling stability of the M-FeS_(2)@CNF anode.In the electrolyte with 3 wt%FEMC,the M-FeS_(2)@CNF anode shows a reversible specific capacity of 592.7 mA h g^(-1)at 0.1 A g^(-1),an excellent rate capability of 327.1 mA h g^(-1)at 5 A g^(-1),and a retention rate 80.7%over 1000 cycles at 1 A g^(-1).More importantly,when assembled with a K_(1.84)Ni[Fe(CN)_(6)]_(0.88)·0.49H_(2)O cathode,the full battery manifests excellent cycle stability and high rate performance.This study demonstrates the significant importance of the synergistic effect of structural regulation and electrolyte optimization in achieving high cycling stability of PIBs.
基金financially supported by Jilin Province Science and Technology Department Program(Nos.YDZJ202201ZYTS304,20220201130GX and 20240101004JJ)the National Natural Science Foundation of China(Nos.52171210 and 52471229)the Science and Technology Project of Jilin Provincial Education Department(No.JJKH20220428KJ)
文摘The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.
基金funded by National Natural Science Foundation of China (22379072, 92372111, 22179070)the Startup Foundation for Introducing Talent of NUIST (2022r038)+1 种基金the Jiangsu Specially Appointed Professor Program, the Natural Science Foundation of Jiangsu Province (BK20220073)the Fundamental Research Funds for the Central Universities (RF1028623157)。
文摘Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) with weak solvation structures is established by the multi-anion strategy.Multiple anions in the electrolyte strengthen the anion-solvent interactions through stronger ion–dipole interactions.This reduces the quantity of free solvent and improves the reduction resistance of solvents.In addition,the Li ion–solvent interaction is weakened,facilitating the anions to enter the solvation sheaths of Li ions.This multi-anion-dominated weak solvation structures boost Li ion diffusion in the electrolyte,accelerate the desolvation process of Li ions,and induce inorganic-rich solid electrolyte interphase and uniform Li deposition.An average Coulombic efficiency of 99.1%for repeated Li plating/stripping can be achieved.Li||LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cells with a high cathode loading of 3.0 m A h cm^(-2) can maintain a capacity retention as high as 95% after 150 cycles.This finding provides novel standpoints to modulate the interaction of solvation structures and extend the lifespan of high-energy–density Li metal batteries.
基金supported by the National Natural Science Foundation of China(22179149,22075329,51573215,and 21978332)Research and Development Project of Henan Academy Sciences China(232018002)。
文摘Single ion gel polymer electrolyte has the advantages of high Li^(+)conductivity and dendrite mitigation.However,the addition of organic solvent makes the electrolyte flammable,posing serious safety hazards.Herein,we report a flame-retard ant cross-linked sp^(3)boron-based single-ion gel polymer electrolyte(BSIPE).BSIPE was prepared by a simple one-step photoinitiated in situ thiol-ene click reaction.Due to the boron-based anions being immobilized in the cross-linking network,the developed BSIPE/PFN exhibits a high t_(Li^(+))(0.87),which can mitigate concentration polarization phenomenon and suppress the growth of lithium dendrites.BSIPE/PFN plasticized with triethyl phosphate(TEP),fluoroethylene carbonate(FEC)and LiNO_(3)exhibits enhanced ionic conductivity of 4.25×10^(-4)S cm^(-1)at 30℃ and flame retardancy.FEC and LiNO_(3) are conducive to form a stable solid electrolyte interphase(SEI)rich in Li_(3)N and LiF to improve interface stability.As expected,the dendrite-free Li‖BSIPE/PFN‖Li symmetric cell exhibits considerable cycling life over 1500 h.BSIPE/PFN significantly boosts the performance of LFP‖Li cell,which displays a capacity retention of 84.6%after 500 cycles.The BSIPE/PFN has promising applications in highsafety and high-performance lithium metal batteries.
基金supported by grants from the National Natural Science Foundation of China(Nos.52072136,52172229,52272201,52302303,51972257)Yanchang Petroleum-WHUT Joint Program(No.yc-whlg-2022ky-05)Fundamental Research Funds for the Central Universities(Nos.104972024RSCrc0006,2023IVA106)for financial support。
文摘Sulfide solid electrolytes with an ultrahigh ionic conductivity are considered to be extremely promising alternatives to liquid electrolytes for next-generation lithium batteries.However,it is difficult to obtain a thin solid electrolyte layer with good mechanical properties due to the weak binding ability between their powder particles,which seriously limits the actual energy density of sulfide all-solid-state lithium batteries(ASSLBs).Fortunately,the preparation of sulfide-polymer composite solid electrolyte(SPCSE)membranes by introducing polymer effectively reduces the thickness of solid electrolytes and guarantees high mechanical properties.In this review,recent progress of SPCSE membranes for ASSLBs is summarized.The classification of components in SPCSE membranes is first introduced briefly.Then,the preparation methods of SPCSE membranes are categorized according to process characteristics,in which the challenges of different methods and their corresponding solutions are carefully reviewed.The energy densities of the full battery composed of SPCSE membranes are further given whenever available to help understanding the device-level performance.Finally,we discuss the potential challenges and research opportunities for SPCSE membranes to guide the future development of high-performance sulfide ASSLBs.
基金the financial support from the 261 Project of MIITNatural Science Foundation of Jiangsu Province(No.BK20240179)。
文摘Fluoropolymers promise all-solid-state lithium metal batteries(ASLMBs)but suffer from two critical challenges.The first is the trade-off between ionic conductivity(σ)and lithium anode reactions,closely related to high-content residual solvents.The second,usually consciously overlooked,is the fluoropolymer's inherent instability against alkaline lithium anodes.Here,we propose indium-based metal-organic frameworks(In-MOFs)as a multifunctional promoter to simultaneously address these two challenges,using poly(vinylidene fluoride-hexafluoropropylene)(PVH)as the typical fluoropolymer.In-MOF plays a trio:(1)adsorbing and converting free residual solvents into bonded states to prevent their side reactions with lithium anodes while retaining their advantages on Li~+transport;(2)forming inorganic-rich solid electrolyte interphase layers to prevent PVH from reacting with lithium anodes and promote uniform lithium deposition without dendrite growth;(3)reducing PVH crystallinity and promoting Li-salt dissociation.Therefore,the resulting PVH/In-MOF(PVH-IM)showcases excellent electrochemical stability against lithium anodes,delivering a 5550 h cycling at 0.2 m A cm^(-2)with a remarkable cumulative lithium deposition capacity of 1110 m Ah cm^(-2).It also exhibits an ultrahighσof 1.23×10^(-3)S cm^(-1)at 25℃.Moreover,all-solid-state LiFePO_4|PVH-IM|Li full cells show outstanding rate capability and cyclability(80.0%capacity retention after 280 cycles at 0.5C),demonstrating high potential for practical ASLMBs.
文摘The growth of dendrites and the side reactions occurring at the Zn anode pose significant challenges to the commercialization of aqueous Zn-ion batteries(AZIBs). These challenges arise from the inherent conflict between mass transfer and electrochemical kinetics. In this study, we propose the use of a multifunctional electrolyte additive based on the xylose(Xylo) molecule to address these issues by modulating the solvation structure and electrode/electrolyte interface, thereby stabilizing the Zn anode. The introduction of the additive alters the solvation structure, creating steric hindrance that impedes charge transfer and then reduces electrochemical kinetics. Furthermore, in-situ analyses demonstrate that the reconstructed electrode/electrolyte interface facilitates stable and rapid Zn^(2+)ion migration and suppresses corrosion and hydrogen evolution reactions. As a result, symmetric cells incorporating the Xylo additive exhibit significantly enhanced reversibility during the Zn plating/stripping process, with an impressively long lifespan of up to 1986 h, compared to cells using pure ZnSO4electrolyte. When combined with a polyaniline cathode, the full cells demonstrate improved capacity and long-term cyclic stability. This work offers an effective direction for improving the stability of Zn anode via electrolyte design, as well as highperformance AZIBs.
基金supported by Hainan Provincial Joint Project of Sanya Yazhou Bay Science and Technology City(No.2021JJLH0069)the Project of Sanya Yazhou Bay Science and Technology City(No.SCKJ-JYRC-2023-55)Hainan Provincial Natural Science Foundation of China(No.522CXTD516).
文摘Zinc perchlorate(Zn(ClO_(4))_(2))electrolytes have demonstrated favorable low-temperature performance in aqueous zinc-ion batteries(AZIBs).However,the Zn anode encounters serious dendrite formation and parasitic reactions in zinc perchlorate electrolytes,which is caused by the fast corrosive kinetics at room temperature.Herein,a concentrated perchlorate-based electrolyte consisting of 4.0 M Zn(ClO_(4))_(2)and saturated NaClO_(4)solution is developed to achieve dendrite-free and stable AZIBs at room temperature.The ClO_(4)−participates in the primary solvation sheath of Zn^(2+),facilitating the in situ formation of Zn_(5)(OH)_(8)Cl_(2)·H_(2)O-rich solid electrolyte interphase(SEI)to suppress the corrosion effect of ClO_(4)^(−).The Zn anode protected by the SEI achieves stable Zn plating/stripping over 3000 h.Furthermore,the MnO_(2)||Zn full cells manifest a stable specific capacity of 200 mAh·g^(−1)at 28℃and 101 mAh·g^(−1)at−20℃.This work introduces a promising approach for boosting the room-temperature performance of perchlorate-based electrolytes for AZIBs.
基金supported by the Natural Science Foundation of China(22379073,52373275)the Natural Science Foundation of Tianjin,China(18JCZDJC31400)the Ministry of Education Innovation Team(IRT13022).
文摘Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a stable solid electrolyte interphase(SEI)layer is a great challenge for QSPE-based lithium(Li)metal batteries(LMBs).Herein,unlike previously reports that the reconstruction of Li^(+)solvation structures in QSPE requires time-consuming bottom-up polymer synthesis,in current study,a facile approach has been developed to reconstruct the Li^(+)solvation structures in QSPE by adjustment of the salt concentrations.The high proportion of Li^(+)-anion complexes can effectively accelerate interfacial Li^(+)diffusion,mitigate the decompositions of organic solvents and induce the formation of a LiF-rich SEI layer,contributing to suppressed Li-dendrite growth.As a result,the Li/QSPE-3/LiFePO_(4)(LFP)cell performs an ultralong lifespan with capacity retention of 77.4%over 3000 cycles at 1 C.With a high-voltage LiCoO_(2)cathode,the cell can stably cycle over 200 cycles at 25℃(capacity retention of∼83.8%).With accelerated ion transport dynamics due to the reconstructed Li^(+)solvation structure,the QSPE-3(the salt concentration is 3 M)is applicable in a wide temperature range.The Li/QSPE-3/LFP full cell exhibits 58.1%and 102.6%of discharge capacity at−15 and 90℃,respectively,compared to those operated at 25℃This study demonstrates a facile yet effective approach on enhancing electrode/electrolyte interfacial stability,enabling the LMBs with simultaneously enhanced safety and high energy density.
