Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving...Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.展开更多
With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial c...With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.展开更多
Lithium-sulfur(Li-S) batteries have been considered as one of the most promising candidates to traditional lithium ion batteries due to its low cost,high theoretical specific capacity(1675 mAh g^(-1)) and energy densi...Lithium-sulfur(Li-S) batteries have been considered as one of the most promising candidates to traditional lithium ion batteries due to its low cost,high theoretical specific capacity(1675 mAh g^(-1)) and energy density(2600 Wh kg^(-1)) of sulfur.Compared with traditional liquid electrolytes,polymer electrolytes(PEs) are ever-increasingly preferred due to their higher safety,superior compatibility,long cycling stability and so on.Despite some progresses on PEs,however,there remain lots of hurdles to be addressed prior to commercial applications.This review begins with native advantages for PEs to replace LEs,and then proposes the ideal requirements for PEs.Furthermore,a brief development history of typical PEs for Li-S batteries is presented to systematically summarize the recent achievements in Li-S batteries with PEs.Noted that the structure-performance relationships of polymer matrixes for PEs are highlighted.Finally,the challenges and opportunities on the future development of PEs are presented.We hold the view that composite polymer electrolytes in virtue of the high ionic conductivity and the compatible interfacial property will be promising solution for high performance Li-S 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
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
Zinc metal batteries(ZMBs)are considered to be promising energy storage devices in the field of largescale energy storage due to the advantages of high energy density,good safety and environmental friendliness.However...Zinc metal batteries(ZMBs)are considered to be promising energy storage devices in the field of largescale energy storage due to the advantages of high energy density,good safety and environmental friendliness.However,the commercialization of ZMBs has been hampered because of the problems caused by aqueous electrolytes,such as hydrogen evolution reaction,electrolyte leakage,and water evaporation.Gel polymer electrolytes(GPEs)have attracted extensive attention due to the features of high security and low water content.However,the disadvantages of poor ion transport rate,easily freezing at low temperature and low mechanical strength are not conducive to the rapid development and practical application of ZMBs.The rational design and fabrication of multifunctional polymer-based frameworks are considered to be effective strategy to obtain high-performance GPEs.In this review,the recent advancements of GPEs with various polymers are generalized.The strategies for the improvement of ionic conductivity,low temperature resistance and mechanical strength of these GPEs,such as adding inorganic fillers,building double cross-linked networks and introducing functional groups,are summarized.The effects of the GPEs on the self-healable ability,inhibiting dendrite growth,and cycling stability of the ZMBs are also discussed.Finally,the key problems and development prospects of GPEs are proposed,which will provide possibility for the further development of GPEs.展开更多
The pursuit of safer energy storage systems is driving the development of advanced electrolytes for lithium-ion batteries.Traditional liquid electrolytes pose flammability risks,while solid-state alternatives often su...The pursuit of safer energy storage systems is driving the development of advanced electrolytes for lithium-ion batteries.Traditional liquid electrolytes pose flammability risks,while solid-state alternatives often suffer from low ionic conductivity.Gel polymer electrolytes(GPEs)emerge as a promising compromise,combining the safety of solids with the ionic conductivity of liquids.Cellulose,an abundant and eco-friendly polymer,presents an ideal base material for sustainable GPEs due to its biocompatibility and mechanical strength.This study systematically investigates how drying methods affect cellulose-based GPEs.Cellulose hydrogels were synthesized through dissolution-crosslinking and processed using vacuum drying(VD),supercritical drying(SCD),and freeze-drying(FD).VD and SCD produced dense membranes with excellent mechanical strength(7.2 MPa)but limited electrolyte uptake(30%–40%).In contrast,FD created a highly porous structure(21.13%porosity)with remarkable electrolyte absorption(638%),leading to superior ionic conductivity(1.22 mS⋅cm^(-1))and lithium-ion transference number(0.28).However,this came at the cost of increased interfacial impedance and poor rate capability,resulting in 81.24%capacity retention after 100 cycles.These findings illuminate the critical balance between electrochemical performance and mechanical properties in cellulose GPEs,providing valuable insights for designing sustainable electrolytes for flexible electronics and electric vehicles.展开更多
Polymeric materials have emerged as a promising alternative to electrolytic solutions in energy storage applications.However,high crystallinity and poor ionic conductivity are the main barriers restricting their daily...Polymeric materials have emerged as a promising alternative to electrolytic solutions in energy storage applications.However,high crystallinity and poor ionic conductivity are the main barriers restricting their daily application.In this study,we propose a polymer electrolyte system consisting of methylcellulose-polyvinyl alcohol(MC-PVA)blend as host material and lithium trifluoromethanesulfonate(LiCF_(3)SO_(3))as dopant,which was prepared using the solution-casting method.The electrochemical impedance spectroscopy(EIS)analysis revealed a maximum conductivity of 5.42×10^(−6) S cm^(−1) with 40 wt.%LiCF_(3)SO_(3).The key findings demonstrated that the variation in the dielectric loss(εi)and dielectric constant(εr)was significantly correlated with the variation in ionic conductivity.Fourier-transform infrared spectroscopy(FTIR)analysis was done to analyse the salt-polymer interaction by observing the shifting of selected bands.By deconvoluting FTIR spectra in the wavenumber range of 970–1100 cm^(−1),transport properties of electrolytes were investigated and found to be improved when the salt concentration was increased to 40 wt.%.Results from the X-ray diffraction(XRD)study suggested that the higher salt concentration promoted the formation of an amorphous phase,which is favourable for ionic conduction.Field emission scanning electron microscopy(FESEM)study demonstrated that the addition of salt altered the surface morphology of MC-PVA.展开更多
Despite the growing interest in fast-cha rging solid-state lithium(Li)-metal batteries(SSLMBs),their practical implementation has yet to be achieved,primarily due to an incomplete understanding of the disparate and of...Despite the growing interest in fast-cha rging solid-state lithium(Li)-metal batteries(SSLMBs),their practical implementation has yet to be achieved,primarily due to an incomplete understanding of the disparate and often conflicting requirements of the bulk electrolyte and the electrode-electrolyte interphase.Here,we present a weakly coordinating cationic polymer electrolyte(WCPE)specifically designed to regulate the Li^(+)coordination structure,thereby enabling fast-charging SSLMBs.The WCPE comprises an imidazolium-based polycationic matrix combined with a succinonitrile(SN)-based highconcentration electrolyte.Unlike conventional neutral polymer matrices,the polycationic matrix in the WCPE competes with Li^(+)for interactions with SN,weakening the original coordination between SN and Li^(+).This modulation of SN-Li^(+)interaction improves both Li^(+)conductivity of the WCPE(σ_(Li^(+))=1.29mS cm^(-1))and redox kinetics at the electrode-electrolyte interphase.Consequently,SSLMB cells(comprising LiFePO_(4)cathodes and Li-metal anodes)with the WCPE achieve fast-charging capability(reaching over 80%state of charge within 10 min),outperforming those of previously reported polymer electrolytebased SSLMBs.展开更多
Solid electrolytes are the most promising candidate for replacing liquid electrolytes due to their safetyand chemical stability advantages. However, a single inorganic or organic solid electrolyte cannot meetthe requi...Solid electrolytes are the most promising candidate for replacing liquid electrolytes due to their safetyand chemical stability advantages. However, a single inorganic or organic solid electrolyte cannot meetthe requirements of commercial all-solid-state batteries (ASSBs), which motivates the composite polymerelectrolyte (CPE). Herein, a CPE of boron nitride nanofiber (BNNF) with a high specific surface area, richpore structure, and poly (ethylene oxide) (PEO) are reported. Anions strongly adsorb on the surface ofBNNF through electrostatic interactions based on oxygen vacancies, promoting the dissociation of lithiumsalts at the two-phase interface. The three-dimensional (3D) BNNF network provides three advantagesin the CPE, including (i) improving ionic conductivity through strong interaction between polymers andfillers, (ii) improving mechanical properties through weaving a robust skeleton, and (iii) improving stability through a rapid and uniform thermal dispersion pathway. Therefore, the CPE with BNNF delivers highionic conduction of 4.21 × 10^(−4) S cm^(−1) at 60 ℃ and excellent cycling stability (plating/stripping cyclesfor 2000 h with a low overpotential of ∼40 mV), which results in excellent electrochemical performanceof LiFePO_(4) (LFP) full cell assembled with CPE-5BNNF-1300 (152.7 mAh g^(−1) after 200 cycles at 0.5 C, and134.8 mAh g^(−1) at 2.0 C). Furthermore, when matched with high-voltage LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2) (NCM622), italso exhibits an outstanding rate capacity of 120.4 mAh g^(−1) at 1.0 C. This work provides insight into theBNNF composite electrolyte and promotes its practical application for ASSBs.展开更多
As a potential substitute for traditional nonaqueous organic electrolytes,polymer-based solid-state electrolytes(SSEs)have the advantages of high safety,flexibility,low density,and easy processing.In contrast,they sti...As a potential substitute for traditional nonaqueous organic electrolytes,polymer-based solid-state electrolytes(SSEs)have the advantages of high safety,flexibility,low density,and easy processing.In contrast,they still face challenges,such as low room-temperature ionic conductivity,narrow electrochemical windows,and poor mechanical strength.To realize the practical application of all-solid-state alkali metal ion batteries,there has been a lot of research on modifying the chemical composition or structure of polymerbased SSEs.In this review,the transport mechanism of alkali metal ions in polymer SSEs is briefly introduced.We systematically summarize the recent strategies to improve polymer-based SSEs,which have been validated in lithium-ion batteries and sodium-ion batteries,including lamellar electrolyte structure,dual salts hybridization,oriented filler alignment,and so on.Then,taking the unique properties of potassium metal and potassium ions into consideration,the feasibility of potassium-ion batteries for practical use enabled by these novel modification methods is discussed.展开更多
Gel polymer electrolytes(GPEs)present the best compromise between mechanical and electrochemical properties,as well as an improvement of the cell safety in the framework of Li metal batteries production.However,the po...Gel polymer electrolytes(GPEs)present the best compromise between mechanical and electrochemical properties,as well as an improvement of the cell safety in the framework of Li metal batteries production.However,the polymerization mechanism typically employed relies on the presence of an initiator,and is hindered by oxygen,thus impeding the industrial scale-up of the GPEs production.In this work,an UV-mediated thiol-ene polymerization,employing polyethylene glycol diacrylate(PEGDA)as oligomer,was carried out in a liquid electrolyte solution(1M LiTFSI in EC/DEC)to obtain a self-standing GPE.A comparative study between two different thiol-containing crosslinkers(trimethylolpropane tris(3-mercaptopropionate)-T3 and pentaerythritol tetrakis(3-mercaptopropionate)-T4)was carried out,studying the effects of the crosslinking environment and the GPE production methods on the cell performances.All the produced GPEs present an excellent room temperature ionic conductivity above 1 mS cm^(-1),as well as a wide electrochemical stability window up to 4.59 V.When cycled at a current density of C/10 for more than 250 cycles,all of the tested cells showed a stable cycling profile and a specific capacity>100 mAh g^(-1),indicating the suitability of such processes for up-scaling.展开更多
To study the behavior of structural dynamics,ionic conductivity and ion transport properties,the gel polymer electrolytes(GPEs)was developed using polyvinyl alcohol in combination with potassium iodide,dimethyl sulfox...To study the behavior of structural dynamics,ionic conductivity and ion transport properties,the gel polymer electrolytes(GPEs)was developed using polyvinyl alcohol in combination with potassium iodide,dimethyl sulfoxide,ethylene carbonate,propylene carbonate and tetra-N-propylammonium iodide(C12H28IN),The GPEs were synthesized via a solution mixing technique,systematically varying the tetra-N-propylammonium iodide concentration to optimize ionic transport properties.The gel polymer electrolytes(GPEs)preparation was initially dissolving the potassium iodide and tetra-N-propylammonium iodide in a measured combination of ethylene carbonate,propylene carbonate,and dimethyl sulfoxide within a glass container.Subsequently,polyvinyl alcohol(PVA)was introduced into the salt solution and continuously stirred at 100℃until a uniform mixture was formed.The solution was then allowed to cool to 30℃and resulting GPE exhibited a gel-like consistency.Electrochemical impedance spectroscopy(EIS)was employed to evaluate ionic conductivity,dielectric behavior,and ion transport properties at the temperature of 25℃.X-ray diffraction(XRD)was utilized to investigate the structure of the gel polymer electrolyte.Fourier-transform infrared(FTIR)spectroscopy was applied to describe the structural interactions between salts and polymer in the GPEs.Notably,the gel polymer electrolytes containing 30 wt.%tetra-N-propylammonium iodides exhibited a remarkable ionic conductivity of approximately 9.70 mS cm^(-1)at the temperature of 25℃.展开更多
Conventional liquid electrolytes in lithium-ion batteries(LIBs)pose significant safety risks and interfacial instability,hindering the development of high-energy-density systems.Solid polymer electrolytes(SPEs),partic...Conventional liquid electrolytes in lithium-ion batteries(LIBs)pose significant safety risks and interfacial instability,hindering the development of high-energy-density systems.Solid polymer electrolytes(SPEs),particularly polyethylene oxide(PEO)-based systems,offer enhanced safety but suffer from low room-temperature ionic conductivity due to high crystallinity,alongside limitations such as poor lithium-ion transference numbers and dendrite growth.To address these challenges,this study develops a novel composite solid electrolyte(PSPH)by synthesizing a polystyrene-polyethylene oxide-polystyrene(PSPEO-PS)triblock copolymer and blending it with poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)and lithium bis(trifluoromethylsulfonyl)imide(LiTFSI).The rigid PS segments suppress PEO crystallization,while PVDF-HFP enhances amorphous domain content,promotes LiTFSI dissociation via its high dielectric constant,and improves mechanical strength.The optimized PSPH composition(M_(w,PEO)=35 kg·mol^(-1),w_(PS)=15%,w_(PVDF-HFP)=30%)exhibits a high ionic conductivity of 1.05×10^(-4) S·cm^(-1)at 25℃,a Li^(+)transference number of 0.46,and an extended electrochemical stability window up to 4.8 V.PSPH demonstrates excellent thermal stability(decomposition onset at about 340℃),flexibility,and interfacial compatibility.LiFePO_(4)/PSPH/Li cells delivere a high discharge capacity of 163.7 mAh·g^(-1) at 0.1 C,with 96.2%capacity retention and 99.83%average coulombic efficiency after 200 cycles.Furthermore,Li/PSPH/Li symmetric cells exhibit stable cycling for over 1500 h at 0.05 mA·cm^(-2) with low overpotential(about 0.15 V).These results demonstrate that PSPH is a highly promising electrolyte for enhancing the safety and electrochemical performance of all-solid-state lithium-metal batteries(LMBs).展开更多
Solid polymer electrolytes(SPEs)have garnered considerable interest in the field of lithium metal batteries(LMBs)owing to their exceptional mechanical strength,excellent designability,and heightened safety characteris...Solid polymer electrolytes(SPEs)have garnered considerable interest in the field of lithium metal batteries(LMBs)owing to their exceptional mechanical strength,excellent designability,and heightened safety characteristics.However,their inherently low ion transport efficiency poses a major challenge for their application in LMBs.To address this issue,covalent organic framework(COF)with their ordered ion transport channels,chemical stability,large specific surface area,and designable multifunctional sites has shown promising potential to enhance lithium-ion conduction.Here,we prepared an anionic COF,Tp Pa-COOLi,which can catalyze the ring-opening copolymerization of cyclic lactone monomers for the in situ fabrication of SPEs.The design leverages the high specific surface area of COF to facilitate the absorption of polymerization precursor and catalyze the polymerization within the pores,forming additional COF-polymer junctions that enhance ion transport pathways.The partial exfoliation of COF achieved through these junctions improved its dispersion within the polymer matrix,preserving ion transport channels and facilitating ion transport across COF grain boundaries.By controlling variables to alter the crystallinity of Tp Pa-COOLi and the presence of-COOLi substituents,Tp Pa-COOLi with partial long-range order and-COOLi substituents exhibited superior electrochemical performance.This research demonstrates the potential in constructing high-performance SPEs for LMBs.展开更多
While single-ion conducting solid polymer electrolytes(SPE)offer inherent safety advantages for lithium metal batteries,their practical implementation is hindered by inadequate ionic transport and unstable electrode i...While single-ion conducting solid polymer electrolytes(SPE)offer inherent safety advantages for lithium metal batteries,their practical implementation is hindered by inadequate ionic transport and unstable electrode interfaces.We presented a breakthrough single-ion SPE system through molecular engineering of lithium-enriched porous aromatic frameworks(PAF-228-Li)integrated with poly(ethylene oxide),achieving exceptional ion conduction and interfacial stability.The precisely designed PAF-228-Li architecture established continuous 3D Li+transport pathways through its intrinsic porous channels and surface conduction sites,synergistically enhanced by PVDF-HFP nanofiber networks.This unique design enabled record-high ionic conductivities of 5.48×10^(-4)S cm^(-1)at 30℃and 3.4×10^(-4)S cm^(-1)at-20℃—among the best reported for PEO-based SPEs.The electrolyte spontaneously formed a selflimiting SEI rich in LiF/Li3N,effectively suppressing dendritic growth while enabling unprecedented cycling stability:Li||LiFePO4cells maintain 83.7%capacity over 700 cycles(30℃)and deliver 104.4 mA h g^(-1)after 1100 cycles at-20℃.Practical viability is further demonstrated in pouch cell configurations with stable operation at 30℃.This work pioneers a materials paradigm combining porous framework engineering with polymer electrolyte design,establishing new researching direction for low-temperature compatible,dendrite-resistant solid-state batteries.展开更多
The development of flexible supercapacitors(FSCs) capable of operating at high temperatures is crucial for expanding the application areas and operating conditions of supercapacitors. Gel polymer electrolytes and elec...The development of flexible supercapacitors(FSCs) capable of operating at high temperatures is crucial for expanding the application areas and operating conditions of supercapacitors. Gel polymer electrolytes and electrode materials stand as two key components that significantly impact the efficacy of hightemperature-tolerant FSCs(HT-FSCs). They should not only exhibit high electrochemical performance and excellent flexibility, but also withstand intense thermal stress. Considerable efforts have been devoted to enhancing their thermal stability while maintaining high electrochemical and mechanical performance. In this review, the fundamentals of HT-FSCs are outlined. A comprehensive overview of state-of-the-art progress and achievements in HT-FSCs, with a focus on thermally stable gel polymer electrolytes and electrode materials is provided. Finally, challenges and future perspectives regarding HT-FSCs are discussed, alongside strategies for elevating operational temperatures and performance.This review offers both theoretical foundations and practical guidelines for designing and manufacturing HT-FSCs, further promoting their widespread adoption across diverse fields.展开更多
Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges ...Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges in mitigating uneven lithium plating/stripping and dendrite growth.Previous efforts primarily focused on passive approaches to mechanically constrain lithium dendrite growth.Recent studies have revealed the significance and effectiveness of regulating supramolecular interactions between polymer chains and other electrolyte components for homogenizing lithium deposition and enhancing the interfacial stability.This report provides a timely critical review to cover recent inspiring advancements in this direction.We first summarize the origins of supramolecular interaction origins,strength-determining factors,and structure–property relationships to establish quantitative correlations between polymer composition and supramolecular interaction properties.Then the recent advances in regulating supramolecular interaction chemistry are comprehensively discussed,focusing on those towards accelerated mass transport and stabilized anode-electrolyte interface.Finally,the remaining challenges are highlighted,and potential future directions in supramolecular interaction regulation of polymer electrolytes are prospected for the practical application of LMBs.展开更多
One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible p...One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible phases.Nevertheless,the regulation of intermolecular interactions between plasticizers and rigid and flexible phases has been largely overlooked.Here,an intermolecular interaction engineering strategy is carried out with well-chosen dual-plasticize within qua si-sol id-state polymer electrolytes(QSPEs).Succinonitrile exhibits a stronger affinity towards rigid phase hydrogenated nitrile butadiene rubber(HNBR),while propene carbonate demonstrates a stronger affinity towards flexible segments poly(propylene carbonate)(PPC).This tailored intermolecular interaction engineering allows for differential plasticization of the polymer's rigid and flexible phases,thereby achieving a balance between ionic conductivity and mechanical strength.The QSPE have both higher ionic conductivity(1.04×10^(-4)S cm^(-1)at 30℃),t_(Li+)(0.55),and tensile strength(0.76 MPa).Li//Li symmetric cells maintaining performance over1100 h at 0.1 mA cm^(-2)and Li//LiFePO_(4)cells retaining 85.0%capacity after 700 cycles at 1.0 C.It is a unique angle to employ intermolecular interaction engineering in QSPEs through dual-plasticizer approach combined with CO_(2)-based polymer materials.This sustainable strategy combining dual-plasticizer engineering with CO_(2)-based polymers,offers insights for designing high-performance,eco-friendly lithium metal batteries.展开更多
Alkali metal batteries(AMBs)have undergone substantial development in portable devices due to their high energy density and durable cycle performance.However,with the rising demand for smart wearable electronic device...Alkali metal batteries(AMBs)have undergone substantial development in portable devices due to their high energy density and durable cycle performance.However,with the rising demand for smart wearable electronic devices,a growing focus on safety and durability becomes increasingly apparent.An effective strategy to address these increased requirements involves employing the quasi-solid gel electrolytes(QSGEs).This review focuses on the application of QSGEs in AMBs,emphasizing four types of gel electrolytes and their influence on battery performance and stability.First,self-healing gels are discussed to prolong battery life and enhance safety through self-repair mechanisms.Then,flexible gels are explored for their mechanical flexibility,making them suitable for wearable devices and flexible electronics.In addition,biomimetic gels inspired by natural designs are introduced for high-performance AMBs.Furthermore,biomass materials gels are presented,derived from natural biomaterials,offering environmental friendliness and biocompatibility.Finally,the perspectives and challenges for future developments are discussed in terms of enhancing the ionic conductivity,mechanical strength,and environmental stability of novel gel materials.The review underscores the significant contributions of these QSGEs in enhancing AMBs performance,including increased lifespan,safety,and adaptability,providing new insights and directions for future research and applications in the field.展开更多
基金the financial support from the National Natural Science Foundation of China(52203123 and 52473248)State Key Laboratory of Polymer Materials Engineering(sklpme2024-2-04)+1 种基金the Fundamental Research Funds for the Central Universitiessponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.
基金supported by the National Natural Science Foundation of China(52103299)。
文摘With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.
基金financially supported by the National Key R&D Program of China(2017YFE0127600)the Science Foundation for the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA22010600)+3 种基金the Key-Area Research and Development Program of Guangdong Province(2020B090919005)the Distinguished Young Scholars of China(51625204)the National Natural Science Foundation of China(U1706229,51803230)support by the DICP&QIBEBT(DICP&QIBEBT UN201707)。
文摘Lithium-sulfur(Li-S) batteries have been considered as one of the most promising candidates to traditional lithium ion batteries due to its low cost,high theoretical specific capacity(1675 mAh g^(-1)) and energy density(2600 Wh kg^(-1)) of sulfur.Compared with traditional liquid electrolytes,polymer electrolytes(PEs) are ever-increasingly preferred due to their higher safety,superior compatibility,long cycling stability and so on.Despite some progresses on PEs,however,there remain lots of hurdles to be addressed prior to commercial applications.This review begins with native advantages for PEs to replace LEs,and then proposes the ideal requirements for PEs.Furthermore,a brief development history of typical PEs for Li-S batteries is presented to systematically summarize the recent achievements in Li-S batteries with PEs.Noted that the structure-performance relationships of polymer matrixes for PEs are highlighted.Finally,the challenges and opportunities on the future development of PEs are presented.We hold the view that composite polymer electrolytes in virtue of the high ionic conductivity and the compatible interfacial property will be promising solution for high performance Li-S 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 Natural Science Foundation of China (No. 22075115)the Natural Science Foundation of Jiangsu Province (No. BK20211352)+2 种基金the Natural Science Foundation(No. 22KJA430005) of Jiangsu Education Committee of ChinaJoint Funds of the National Natural Science Foundation of China (No. U2141201)Postgraduate Research&Practice Innovation Program of Jiangsu Province (No. 2024XKT0500)
文摘Zinc metal batteries(ZMBs)are considered to be promising energy storage devices in the field of largescale energy storage due to the advantages of high energy density,good safety and environmental friendliness.However,the commercialization of ZMBs has been hampered because of the problems caused by aqueous electrolytes,such as hydrogen evolution reaction,electrolyte leakage,and water evaporation.Gel polymer electrolytes(GPEs)have attracted extensive attention due to the features of high security and low water content.However,the disadvantages of poor ion transport rate,easily freezing at low temperature and low mechanical strength are not conducive to the rapid development and practical application of ZMBs.The rational design and fabrication of multifunctional polymer-based frameworks are considered to be effective strategy to obtain high-performance GPEs.In this review,the recent advancements of GPEs with various polymers are generalized.The strategies for the improvement of ionic conductivity,low temperature resistance and mechanical strength of these GPEs,such as adding inorganic fillers,building double cross-linked networks and introducing functional groups,are summarized.The effects of the GPEs on the self-healable ability,inhibiting dendrite growth,and cycling stability of the ZMBs are also discussed.Finally,the key problems and development prospects of GPEs are proposed,which will provide possibility for the further development of GPEs.
基金supported by the Natural Science Foundation of China(52063005)Guizhou Province Science and Technology Achievement Transformation Project[2025]general 020Central Guiding Local Science and Technology Development Funds[2024]020 and[2025]013,ZZSG[2024]015,KXJZ[2025]037.
文摘The pursuit of safer energy storage systems is driving the development of advanced electrolytes for lithium-ion batteries.Traditional liquid electrolytes pose flammability risks,while solid-state alternatives often suffer from low ionic conductivity.Gel polymer electrolytes(GPEs)emerge as a promising compromise,combining the safety of solids with the ionic conductivity of liquids.Cellulose,an abundant and eco-friendly polymer,presents an ideal base material for sustainable GPEs due to its biocompatibility and mechanical strength.This study systematically investigates how drying methods affect cellulose-based GPEs.Cellulose hydrogels were synthesized through dissolution-crosslinking and processed using vacuum drying(VD),supercritical drying(SCD),and freeze-drying(FD).VD and SCD produced dense membranes with excellent mechanical strength(7.2 MPa)but limited electrolyte uptake(30%–40%).In contrast,FD created a highly porous structure(21.13%porosity)with remarkable electrolyte absorption(638%),leading to superior ionic conductivity(1.22 mS⋅cm^(-1))and lithium-ion transference number(0.28).However,this came at the cost of increased interfacial impedance and poor rate capability,resulting in 81.24%capacity retention after 100 cycles.These findings illuminate the critical balance between electrochemical performance and mechanical properties in cellulose GPEs,providing valuable insights for designing sustainable electrolytes for flexible electronics and electric vehicles.
基金Universiti Teknologi PETRONAS for the financial support provided through the YUTP-FRG grant(015LC0-631).
文摘Polymeric materials have emerged as a promising alternative to electrolytic solutions in energy storage applications.However,high crystallinity and poor ionic conductivity are the main barriers restricting their daily application.In this study,we propose a polymer electrolyte system consisting of methylcellulose-polyvinyl alcohol(MC-PVA)blend as host material and lithium trifluoromethanesulfonate(LiCF_(3)SO_(3))as dopant,which was prepared using the solution-casting method.The electrochemical impedance spectroscopy(EIS)analysis revealed a maximum conductivity of 5.42×10^(−6) S cm^(−1) with 40 wt.%LiCF_(3)SO_(3).The key findings demonstrated that the variation in the dielectric loss(εi)and dielectric constant(εr)was significantly correlated with the variation in ionic conductivity.Fourier-transform infrared spectroscopy(FTIR)analysis was done to analyse the salt-polymer interaction by observing the shifting of selected bands.By deconvoluting FTIR spectra in the wavenumber range of 970–1100 cm^(−1),transport properties of electrolytes were investigated and found to be improved when the salt concentration was increased to 40 wt.%.Results from the X-ray diffraction(XRD)study suggested that the higher salt concentration promoted the formation of an amorphous phase,which is favourable for ionic conduction.Field emission scanning electron microscopy(FESEM)study demonstrated that the addition of salt altered the surface morphology of MC-PVA.
基金supported by the Basic Science Research Program(RS-2024-00344021,RS-2023-00261543,and RS-202300257666)through the National Research Foundation of Korea(NRF),the National Research Council of Science(000)Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea Government(MOTIE)(RS-2024-00420590,HRD Program for Industrial Innovation)The computational resources were provided by KITSI(KSC-2024-CRE-0143)。
文摘Despite the growing interest in fast-cha rging solid-state lithium(Li)-metal batteries(SSLMBs),their practical implementation has yet to be achieved,primarily due to an incomplete understanding of the disparate and often conflicting requirements of the bulk electrolyte and the electrode-electrolyte interphase.Here,we present a weakly coordinating cationic polymer electrolyte(WCPE)specifically designed to regulate the Li^(+)coordination structure,thereby enabling fast-charging SSLMBs.The WCPE comprises an imidazolium-based polycationic matrix combined with a succinonitrile(SN)-based highconcentration electrolyte.Unlike conventional neutral polymer matrices,the polycationic matrix in the WCPE competes with Li^(+)for interactions with SN,weakening the original coordination between SN and Li^(+).This modulation of SN-Li^(+)interaction improves both Li^(+)conductivity of the WCPE(σ_(Li^(+))=1.29mS cm^(-1))and redox kinetics at the electrode-electrolyte interphase.Consequently,SSLMB cells(comprising LiFePO_(4)cathodes and Li-metal anodes)with the WCPE achieve fast-charging capability(reaching over 80%state of charge within 10 min),outperforming those of previously reported polymer electrolytebased SSLMBs.
基金financially supported by the Science and Tech-nology Innovation Base Project(No.226Z3606G)the National Natural Science Foundation of China(No.51802073)+3 种基金the Hebei Province Graduate Student Innovation Ability Training Project(No.CXZZBS2023040)the Hebei Province Eighth Batch of“100 People Plan”Project(No.E2018050008)the Natural Science Foundation of Hebei Province(No.E2018202129)Hebei Key Laboratory of Boron Nitride and Nano Materials.
文摘Solid electrolytes are the most promising candidate for replacing liquid electrolytes due to their safetyand chemical stability advantages. However, a single inorganic or organic solid electrolyte cannot meetthe requirements of commercial all-solid-state batteries (ASSBs), which motivates the composite polymerelectrolyte (CPE). Herein, a CPE of boron nitride nanofiber (BNNF) with a high specific surface area, richpore structure, and poly (ethylene oxide) (PEO) are reported. Anions strongly adsorb on the surface ofBNNF through electrostatic interactions based on oxygen vacancies, promoting the dissociation of lithiumsalts at the two-phase interface. The three-dimensional (3D) BNNF network provides three advantagesin the CPE, including (i) improving ionic conductivity through strong interaction between polymers andfillers, (ii) improving mechanical properties through weaving a robust skeleton, and (iii) improving stability through a rapid and uniform thermal dispersion pathway. Therefore, the CPE with BNNF delivers highionic conduction of 4.21 × 10^(−4) S cm^(−1) at 60 ℃ and excellent cycling stability (plating/stripping cyclesfor 2000 h with a low overpotential of ∼40 mV), which results in excellent electrochemical performanceof LiFePO_(4) (LFP) full cell assembled with CPE-5BNNF-1300 (152.7 mAh g^(−1) after 200 cycles at 0.5 C, and134.8 mAh g^(−1) at 2.0 C). Furthermore, when matched with high-voltage LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2) (NCM622), italso exhibits an outstanding rate capacity of 120.4 mAh g^(−1) at 1.0 C. This work provides insight into theBNNF composite electrolyte and promotes its practical application for ASSBs.
基金Fundamental Research Funds for the Central Universities,Grant/Award Number:FRF-IDRY-21-013National Natural Science Foundation of China,Grant/Award Numbers:52371131,52474318+1 种基金Beijing Nova Program,Grant/Award Number:Z211100002121082State Key Laboratory of Explosion Science and Technology,Grant/Award Number:QNKT23-05。
文摘As a potential substitute for traditional nonaqueous organic electrolytes,polymer-based solid-state electrolytes(SSEs)have the advantages of high safety,flexibility,low density,and easy processing.In contrast,they still face challenges,such as low room-temperature ionic conductivity,narrow electrochemical windows,and poor mechanical strength.To realize the practical application of all-solid-state alkali metal ion batteries,there has been a lot of research on modifying the chemical composition or structure of polymerbased SSEs.In this review,the transport mechanism of alkali metal ions in polymer SSEs is briefly introduced.We systematically summarize the recent strategies to improve polymer-based SSEs,which have been validated in lithium-ion batteries and sodium-ion batteries,including lamellar electrolyte structure,dual salts hybridization,oriented filler alignment,and so on.Then,taking the unique properties of potassium metal and potassium ions into consideration,the feasibility of potassium-ion batteries for practical use enabled by these novel modification methods is discussed.
基金the project PNRR-NGEU,which has received funding from the MUR-DM 352/2022.
文摘Gel polymer electrolytes(GPEs)present the best compromise between mechanical and electrochemical properties,as well as an improvement of the cell safety in the framework of Li metal batteries production.However,the polymerization mechanism typically employed relies on the presence of an initiator,and is hindered by oxygen,thus impeding the industrial scale-up of the GPEs production.In this work,an UV-mediated thiol-ene polymerization,employing polyethylene glycol diacrylate(PEGDA)as oligomer,was carried out in a liquid electrolyte solution(1M LiTFSI in EC/DEC)to obtain a self-standing GPE.A comparative study between two different thiol-containing crosslinkers(trimethylolpropane tris(3-mercaptopropionate)-T3 and pentaerythritol tetrakis(3-mercaptopropionate)-T4)was carried out,studying the effects of the crosslinking environment and the GPE production methods on the cell performances.All the produced GPEs present an excellent room temperature ionic conductivity above 1 mS cm^(-1),as well as a wide electrochemical stability window up to 4.59 V.When cycled at a current density of C/10 for more than 250 cycles,all of the tested cells showed a stable cycling profile and a specific capacity>100 mAh g^(-1),indicating the suitability of such processes for up-scaling.
基金funding from Universiti Sains Malaysia under the Bridging Grant(Project No:R501-LR-RND003-0000002095-0000)to support this study.
文摘To study the behavior of structural dynamics,ionic conductivity and ion transport properties,the gel polymer electrolytes(GPEs)was developed using polyvinyl alcohol in combination with potassium iodide,dimethyl sulfoxide,ethylene carbonate,propylene carbonate and tetra-N-propylammonium iodide(C12H28IN),The GPEs were synthesized via a solution mixing technique,systematically varying the tetra-N-propylammonium iodide concentration to optimize ionic transport properties.The gel polymer electrolytes(GPEs)preparation was initially dissolving the potassium iodide and tetra-N-propylammonium iodide in a measured combination of ethylene carbonate,propylene carbonate,and dimethyl sulfoxide within a glass container.Subsequently,polyvinyl alcohol(PVA)was introduced into the salt solution and continuously stirred at 100℃until a uniform mixture was formed.The solution was then allowed to cool to 30℃and resulting GPE exhibited a gel-like consistency.Electrochemical impedance spectroscopy(EIS)was employed to evaluate ionic conductivity,dielectric behavior,and ion transport properties at the temperature of 25℃.X-ray diffraction(XRD)was utilized to investigate the structure of the gel polymer electrolyte.Fourier-transform infrared(FTIR)spectroscopy was applied to describe the structural interactions between salts and polymer in the GPEs.Notably,the gel polymer electrolytes containing 30 wt.%tetra-N-propylammonium iodides exhibited a remarkable ionic conductivity of approximately 9.70 mS cm^(-1)at the temperature of 25℃.
基金supported by the 2024 Capital Construction Funds within the Provincial Budget of Jilin Provincial Development and Reform Commission[2024C018-2].
文摘Conventional liquid electrolytes in lithium-ion batteries(LIBs)pose significant safety risks and interfacial instability,hindering the development of high-energy-density systems.Solid polymer electrolytes(SPEs),particularly polyethylene oxide(PEO)-based systems,offer enhanced safety but suffer from low room-temperature ionic conductivity due to high crystallinity,alongside limitations such as poor lithium-ion transference numbers and dendrite growth.To address these challenges,this study develops a novel composite solid electrolyte(PSPH)by synthesizing a polystyrene-polyethylene oxide-polystyrene(PSPEO-PS)triblock copolymer and blending it with poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)and lithium bis(trifluoromethylsulfonyl)imide(LiTFSI).The rigid PS segments suppress PEO crystallization,while PVDF-HFP enhances amorphous domain content,promotes LiTFSI dissociation via its high dielectric constant,and improves mechanical strength.The optimized PSPH composition(M_(w,PEO)=35 kg·mol^(-1),w_(PS)=15%,w_(PVDF-HFP)=30%)exhibits a high ionic conductivity of 1.05×10^(-4) S·cm^(-1)at 25℃,a Li^(+)transference number of 0.46,and an extended electrochemical stability window up to 4.8 V.PSPH demonstrates excellent thermal stability(decomposition onset at about 340℃),flexibility,and interfacial compatibility.LiFePO_(4)/PSPH/Li cells delivere a high discharge capacity of 163.7 mAh·g^(-1) at 0.1 C,with 96.2%capacity retention and 99.83%average coulombic efficiency after 200 cycles.Furthermore,Li/PSPH/Li symmetric cells exhibit stable cycling for over 1500 h at 0.05 mA·cm^(-2) with low overpotential(about 0.15 V).These results demonstrate that PSPH is a highly promising electrolyte for enhancing the safety and electrochemical performance of all-solid-state lithium-metal batteries(LMBs).
基金the National Natural Science Foundation of China(grant nos.52020105012 and 523B2025)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003)the Analysis and Testing Center of HUST for the assistance in analysis and testing。
文摘Solid polymer electrolytes(SPEs)have garnered considerable interest in the field of lithium metal batteries(LMBs)owing to their exceptional mechanical strength,excellent designability,and heightened safety characteristics.However,their inherently low ion transport efficiency poses a major challenge for their application in LMBs.To address this issue,covalent organic framework(COF)with their ordered ion transport channels,chemical stability,large specific surface area,and designable multifunctional sites has shown promising potential to enhance lithium-ion conduction.Here,we prepared an anionic COF,Tp Pa-COOLi,which can catalyze the ring-opening copolymerization of cyclic lactone monomers for the in situ fabrication of SPEs.The design leverages the high specific surface area of COF to facilitate the absorption of polymerization precursor and catalyze the polymerization within the pores,forming additional COF-polymer junctions that enhance ion transport pathways.The partial exfoliation of COF achieved through these junctions improved its dispersion within the polymer matrix,preserving ion transport channels and facilitating ion transport across COF grain boundaries.By controlling variables to alter the crystallinity of Tp Pa-COOLi and the presence of-COOLi substituents,Tp Pa-COOLi with partial long-range order and-COOLi substituents exhibited superior electrochemical performance.This research demonstrates the potential in constructing high-performance SPEs for LMBs.
基金supported by the National Natural Science Foundation of China(52473206,U21A20330,52073118)the“111”Project(B18012l)+1 种基金the Shenzhen Science and Technology Plan Funding(JCYJ20230807112800001)the Open Research Funding of State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences(PPCL2024-016)。
文摘While single-ion conducting solid polymer electrolytes(SPE)offer inherent safety advantages for lithium metal batteries,their practical implementation is hindered by inadequate ionic transport and unstable electrode interfaces.We presented a breakthrough single-ion SPE system through molecular engineering of lithium-enriched porous aromatic frameworks(PAF-228-Li)integrated with poly(ethylene oxide),achieving exceptional ion conduction and interfacial stability.The precisely designed PAF-228-Li architecture established continuous 3D Li+transport pathways through its intrinsic porous channels and surface conduction sites,synergistically enhanced by PVDF-HFP nanofiber networks.This unique design enabled record-high ionic conductivities of 5.48×10^(-4)S cm^(-1)at 30℃and 3.4×10^(-4)S cm^(-1)at-20℃—among the best reported for PEO-based SPEs.The electrolyte spontaneously formed a selflimiting SEI rich in LiF/Li3N,effectively suppressing dendritic growth while enabling unprecedented cycling stability:Li||LiFePO4cells maintain 83.7%capacity over 700 cycles(30℃)and deliver 104.4 mA h g^(-1)after 1100 cycles at-20℃.Practical viability is further demonstrated in pouch cell configurations with stable operation at 30℃.This work pioneers a materials paradigm combining porous framework engineering with polymer electrolyte design,establishing new researching direction for low-temperature compatible,dendrite-resistant solid-state batteries.
基金Fundamental Research Funds for the Central Universities of China(Grant No. SWU-KT22030)Scientific and Technological Research Program of Chongqing Municipal Education Commission of China (No.KJQN202300205)financial support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under the project of 457444676。
文摘The development of flexible supercapacitors(FSCs) capable of operating at high temperatures is crucial for expanding the application areas and operating conditions of supercapacitors. Gel polymer electrolytes and electrode materials stand as two key components that significantly impact the efficacy of hightemperature-tolerant FSCs(HT-FSCs). They should not only exhibit high electrochemical performance and excellent flexibility, but also withstand intense thermal stress. Considerable efforts have been devoted to enhancing their thermal stability while maintaining high electrochemical and mechanical performance. In this review, the fundamentals of HT-FSCs are outlined. A comprehensive overview of state-of-the-art progress and achievements in HT-FSCs, with a focus on thermally stable gel polymer electrolytes and electrode materials is provided. Finally, challenges and future perspectives regarding HT-FSCs are discussed, alongside strategies for elevating operational temperatures and performance.This review offers both theoretical foundations and practical guidelines for designing and manufacturing HT-FSCs, further promoting their widespread adoption across diverse fields.
基金support from The Hong Kong Polytechnic University(U-CDCA)and Innovation and Technology Fund(ITS-322-23FP)。
文摘Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges in mitigating uneven lithium plating/stripping and dendrite growth.Previous efforts primarily focused on passive approaches to mechanically constrain lithium dendrite growth.Recent studies have revealed the significance and effectiveness of regulating supramolecular interactions between polymer chains and other electrolyte components for homogenizing lithium deposition and enhancing the interfacial stability.This report provides a timely critical review to cover recent inspiring advancements in this direction.We first summarize the origins of supramolecular interaction origins,strength-determining factors,and structure–property relationships to establish quantitative correlations between polymer composition and supramolecular interaction properties.Then the recent advances in regulating supramolecular interaction chemistry are comprehensively discussed,focusing on those towards accelerated mass transport and stabilized anode-electrolyte interface.Finally,the remaining challenges are highlighted,and potential future directions in supramolecular interaction regulation of polymer electrolytes are prospected for the practical application of LMBs.
基金supported by the National Key Research and Development Program(2019YFA0705701)National Natural Science Foundation of China(22075329,22008267,21978332 and 22179149)+1 种基金Research and Development Project of Henan Academy Sciences China(232018002)Guangdong Basic and Applied Basic Research Foundation(2021A1515010731)。
文摘One effective approach to strike the balance between ionic conductivity and mechanical strength in polymer electrolytes involves the design of a coupled polymer molecular structure comprising both rigid and flexible phases.Nevertheless,the regulation of intermolecular interactions between plasticizers and rigid and flexible phases has been largely overlooked.Here,an intermolecular interaction engineering strategy is carried out with well-chosen dual-plasticize within qua si-sol id-state polymer electrolytes(QSPEs).Succinonitrile exhibits a stronger affinity towards rigid phase hydrogenated nitrile butadiene rubber(HNBR),while propene carbonate demonstrates a stronger affinity towards flexible segments poly(propylene carbonate)(PPC).This tailored intermolecular interaction engineering allows for differential plasticization of the polymer's rigid and flexible phases,thereby achieving a balance between ionic conductivity and mechanical strength.The QSPE have both higher ionic conductivity(1.04×10^(-4)S cm^(-1)at 30℃),t_(Li+)(0.55),and tensile strength(0.76 MPa).Li//Li symmetric cells maintaining performance over1100 h at 0.1 mA cm^(-2)and Li//LiFePO_(4)cells retaining 85.0%capacity after 700 cycles at 1.0 C.It is a unique angle to employ intermolecular interaction engineering in QSPEs through dual-plasticizer approach combined with CO_(2)-based polymer materials.This sustainable strategy combining dual-plasticizer engineering with CO_(2)-based polymers,offers insights for designing high-performance,eco-friendly lithium metal batteries.
基金support from the Postgraduate Research&Practice Innovation Program of Jiangsu Province(Yangzhou University)(KYCX23_3508)the Yangzhou University International Academic Exchange Fund.Prof.Guoxiu Wang acknowledges the Australian Research Council(ARC)Linkage project(LP200200926).
文摘Alkali metal batteries(AMBs)have undergone substantial development in portable devices due to their high energy density and durable cycle performance.However,with the rising demand for smart wearable electronic devices,a growing focus on safety and durability becomes increasingly apparent.An effective strategy to address these increased requirements involves employing the quasi-solid gel electrolytes(QSGEs).This review focuses on the application of QSGEs in AMBs,emphasizing four types of gel electrolytes and their influence on battery performance and stability.First,self-healing gels are discussed to prolong battery life and enhance safety through self-repair mechanisms.Then,flexible gels are explored for their mechanical flexibility,making them suitable for wearable devices and flexible electronics.In addition,biomimetic gels inspired by natural designs are introduced for high-performance AMBs.Furthermore,biomass materials gels are presented,derived from natural biomaterials,offering environmental friendliness and biocompatibility.Finally,the perspectives and challenges for future developments are discussed in terms of enhancing the ionic conductivity,mechanical strength,and environmental stability of novel gel materials.The review underscores the significant contributions of these QSGEs in enhancing AMBs performance,including increased lifespan,safety,and adaptability,providing new insights and directions for future research and applications in the field.
