Since the advent of the solid-state batteries,employing solid polymer electrolytes(SPEs)to replace routine flammable liquid electrolytes is regarded to be one of the most promising solutions in pursing highenergy-dens...Since the advent of the solid-state batteries,employing solid polymer electrolytes(SPEs)to replace routine flammable liquid electrolytes is regarded to be one of the most promising solutions in pursing highenergy-density battery systems.SPEs with superior thermal stability,good processability,and high mechanical modulus obtain increasing attentions.However,SPE-based batteries are not impenetrable due to their decomposition and combustibility under extreme conditions.Researchers believe incorporating appropriate flame-retardant additives/solvents/fragments into SPEs can intrinsically reduce their flammability to solve the battery safety issues.In this review,the recent research progress of incombustible SPEs,with special emphasis on flame-retardant structural design,is summarized.Specifically,a brief introduction of flame-retardant mechanism,evaluation index for safety of SPEs,and a detailed overview of the latest advances on diverse-types SPEs in various battery systems are highlighted.The deep insight into thermal ru naway process,the free-standing incombustible GPEs,and the ratio nal design of pouch cell structures may be the main directions to motivate revolutionary next-generation for safety batteries.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteri...Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.展开更多
Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked pol...Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.展开更多
All-solid-state lithium(Li)metal batteries(ASSLMBs)are considered one of the most promising secondary batteries due to their high theoretical capacity and high safety performance.However,low room-temperature ionic con...All-solid-state lithium(Li)metal batteries(ASSLMBs)are considered one of the most promising secondary batteries due to their high theoretical capacity and high safety performance.However,low room-temperature ionic conductivity and poor interfacial stability are two key factors affecting the practical application of ASSLMBs,and our understanding of the mechanisms behind these key problems from microscopic perspective is still limited.In this review,the mechanisms and advanced characterization techniques of ASSLMBs are summarized to correlate the microstructures and properties.Firstly,we summarize the challenges faced by solid polymer electrolytes(SPEs)in ASSLMBs,such as the low roomtemperature ionic conductivity and the poor interfacial stability.Secondly,several typical improvement methods of polymer ASSLMBs are discussed,including composite SPEs,ultra-thin SPEs,SPEs surface modification and Li anode surface modification.Finally,we conclude the characterizations for correlating the microstructures and the properties of SPEs,with emphasis on the use of emerging advanced techniques(e.g.,cryo-transmission electron microscopy)for in-depth analyzing ASSLMBs.The influence of the microstructures on the properties is very important.Until now,it has been difficult for us to understand the microstructures of batteries.However,some recent studies have demonstrated that we have a better understanding of the microstructures of batteries.Then we suggest that in situ characterization,nondestructive characterization and sub-angstrom resolution are the key technologies to help us further understand the batteries'microstructures and promote the development of batteries.And potential investigations to understand the microstructures evolution and the batteries behaviors are also prospected to expect further reasonable theoretical guidance for the design of ASSLMBs with ideal performance.展开更多
Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for building solid-state lithium batteries due to their excellent flexibility,scalability,and interfacial compatibility with electro...Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for building solid-state lithium batteries due to their excellent flexibility,scalability,and interfacial compatibility with electrodes.However,the low ionic conductivity and poor cyclic stability of SPEs do not meet the requirements for practical applications of lithium batteries.Here,a novel polymer dispersed ionic liquid-based solid polymer electrolyte(PDIL-SPE)is fabricated using the in situ polymerization-induced phase separation(PIPS)method.The as-prepared PDIL-SPE possesses both outstanding ionic conductivity(0.74 mS cm^(-1) at 25℃)and a wide electrochemical window(up to 4.86 V),and the formed unique three-dimensional(3D)co-continuous structure of polymer matrix and ionic liquid in PDIL-SPE can promote the transport of lithium ions.Also,the 3D co-continuous structure of PDIL-SPE effectively accommodates the severe volume expansion for prolonged lithium plating and stripping processes over 1000 h at 0.5 mA cm^(-2) under 25℃.Moreover,the LiFePO_(4)//Li coin cell can work stably over 150 cycles at a 1 C rate under room temperature with a capacity retention of 90.6%from 111.1 to 100.7 mAh g^(-1).The PDIL-SPE composite is a promising material system for enabling the ultrastable operation of solid-state lithium-metal batteries.展开更多
Electrolytes based on poly(ionic liquid)s(PILs)have attracted great attention in the fields of next-generation solid lithium-ion batteries.However,the low ionic conductivity prevents their practical applications.Herei...Electrolytes based on poly(ionic liquid)s(PILs)have attracted great attention in the fields of next-generation solid lithium-ion batteries.However,the low ionic conductivity prevents their practical applications.Herein,we report novel solid electrolytes based on block copolymers composed of PILs and comb-like poly(ethylene glycol)(PEG),which were synthesized via ring-opening metathesis polymerization of 3-(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1-butyl-1H-imidazol-3-ium bis((trifluoromethyl)sulfonyl)amide and poly(ethylene glycol monomethyl ether)bicyclo[2.2.1]hept-5-ene-2-carboxylate.Comb-like PEG acts as plasticizers in block copolymers dominated by PILs to promote the mobility of PILs segments.Effects of the copolymer composition and length of the comb-like PEG chain on ionic conductivity were investigated.The optimized electrolyte delivers the highest ionic conductivity of 1.5×10^(–5)S·cm^(–1)at 30℃,and robust electrochemical stability up to 4.6 V.A solid-state Li/LiFePO4 cell using the optimized electrolyte demonstrates good cycle performance at 0.2 C with high capacity retention of 92%after 70 cycles at 50℃.展开更多
The rapid development of new energy vehicles and 5G communication technologies has led to higher demands for the safety,energy density,and cycle performance of lithium-ion batteries as power sources.However,the curren...The rapid development of new energy vehicles and 5G communication technologies has led to higher demands for the safety,energy density,and cycle performance of lithium-ion batteries as power sources.However,the currently used liquid carbonate compounds in commercial lithium-ion battery electrolytes pose potential safety hazards such as leakage,swelling,corrosion,and flammability.Solid electrolytes can be used to mitigate these risks and create a safer lithium battery.Furthermore,high-energy density can be achieved by using solid electrolytes along with high-voltage cathode and metal lithium anode.Two types of solid electrolytes are generally used:inorganic solid electrolytes and polymer solid electrolytes.Inorganic solid electrolytes have high ionic conductivity,electrochemical stability window,and mechanical strength,but suffer from large solid/solid contact resistance between the electrode and electrolyte.Polymer solid electrolytes have good flexibility,processability,and contact interface properties,but low room temperature ionic conductivity,necessitating operation at elevated temperatures.Composite solid electrolytes(CSEs) are a promising alternative because they offer light weight and flexibility,like polymers,as well as the strength and stability of inorganic electrolytes.This paper presents a comprehensive review of recent advances in CSEs to help researchers optimize CSE composition and interactions for practical applications.It covers the development history of solid-state electrolytes,CSE properties with respect to nanofillers,morphology,and polymer types,and also discusses the lithium-ion transport mechanism of the composite electrolyte,and the methods of engineering interfaces with the positive and negative electrodes.Overall,the paper aims to provide an outlook on the potential applications of CSEs in solid-state lithium batteries,and to inspire further research aimed at the development of more systematic optimization strategies for CSEs.展开更多
To raise the room temperature ionic conductivity and improve the mechanical strength of a PEO-based polymer electrolyte, a noncrystalline two-component epoxy electrolyte system has been prepared. The diglycidyl ether ...To raise the room temperature ionic conductivity and improve the mechanical strength of a PEO-based polymer electrolyte, a noncrystalline two-component epoxy electrolyte system has been prepared. The diglycidyl ether of polyethylene glycols as precursors of the system were synthesized by a two-step process. The presumed structure of the product was characterized, by ^(13)C, ~1H NMR and IR spectroscopy. It was found that a side-reaction occurred between the secondary hydroxyl group of PEG-chlorohydrin and epichlorohydrin in some degree, resulting in a by- product containing—CH_2Cl side group. By selecting a characteristic signal, which is undistorted by the increase in the length of CH_2 CH_2—O segment, a ~1H NMR approach of determining the equivalent epoxy weight (EEW) was proposed. The method is valid to specimens even though the EEW is as high as 2,000. The examination of the specimens by DSC showed that epoxidation greatly depressed the crystallinity of the PEG's, whereas the T_g was raised.展开更多
Solid polymer electrolytes(SPEs)are one of the most promising alternatives to flammable liquid electrolytes for building safe Li metal batteries.Nevertheless,the poor ionic conductivity at room temperature(RT)and low ...Solid polymer electrolytes(SPEs)are one of the most promising alternatives to flammable liquid electrolytes for building safe Li metal batteries.Nevertheless,the poor ionic conductivity at room temperature(RT)and low resistance to Li dendrites seriously hinder the commercialization of SPEs.Herein,we design a bifunctional flame retardant SPE by combining hydroxyapatite(HAP)nanomaterials with Nmethyl pyrrolidone(NMP)in the PVDF-HFP matrix.The addition of HAP generates a hydrogen bond network with the PVDF-HFP matrix and cooperates with NMP to facilitate the dissociation of Li TFSI in the PVDF-HFP matrix.Consequently,the prepared SPE demonstrates superior ionic conductivity at RT,excellent fireproof properties,and strong resistance to Li dendrites.The assembled Li symmetric cell with prepared SPE exhibits a stable cycling performance of over 1200 h at 0.2 m A cm^(-2),and the solid-state LiFePO_4||Li cell shows excellent capacity retention of 85.3%over 600 cycles at 0.5 C.展开更多
Solid polymer electrolytes(SPEs), such as polyethylene oxide(PEO), are characteristic of good flexibility and excellent processability, but they suffer from low ionic conductivity and small Li+transference number at a...Solid polymer electrolytes(SPEs), such as polyethylene oxide(PEO), are characteristic of good flexibility and excellent processability, but they suffer from low ionic conductivity and small Li+transference number at ambient temperature. Inorganic solid electrolytes(ISEs), garnet-type Li7La3Zr2O12 and its derivatives(LLZO-based) in particular, possess high ionic conductivity at room temperature, wide electrochemical stability window, large Li+transference number as well as good stability against Li metal anode.Nevertheless, lithium dendrites growth, interfacial contact issue and brittle nature of LLZO-based ceramic electrolytes prevent their practical applications. In response to these shortcomings, LLZO-based/polymer solid composite electrolytes(SCEs), taking complementary advantages of two kinds of electrolytes, and thus simultaneously improving the electrode wettability, ionic conductivity and mechanical strength, have been made to develop high-performance SCEs in recent years. Herein, the intrinsic properties and research progress of LLZO-based/polymer SCEs, including LLZO-based/PEO SCEs(LLZO-based/PEO SCEs with uniform dispersion of LLZO-based fillers and LLZO-based/PEO layered SCEs) and LLZO-based/novel polymers SCEs, are summarized. Besides, comprehensive updates on their applications in solid-state batteries are also presented. Finally, challenges and perspectives of LLZO-based/polymer SCEs for advanced allsolid-state lithium batteries(ASSLBs) are suggested. This review paper aims to provide systematic research progress of LLZO-based/polymer SCEs, to allow for more efficient and target-oriented research on improving LLZO-based/polymer SCEs.展开更多
Solid polymer electrolytes(SPEs)have become increasingly attractive in solid-state lithium-ion batteries(SSLIBs)in recent years because of their inherent properties of flexibility,processability,and interfacial compat...Solid polymer electrolytes(SPEs)have become increasingly attractive in solid-state lithium-ion batteries(SSLIBs)in recent years because of their inherent properties of flexibility,processability,and interfacial compatibility.However,the commercialization of SPEs remains challenging for flexible and high-energy-density LIBs.The incorporation of functional additives into SPEs could significantly improve the electrochemical and mechanical properties of SPEs and has created some historical milestones in boosting the development of SPEs.In this study,we review the roles of additives in SPEs,highlighting the working mechanisms and functionalities of the additives.The additives could afford significant advantages in boosting ionic conductivity,increasing ion transference number,improving high-voltage stability,enhancing mechanical strength,inhibiting lithium dendrite,and reducing flammability.Moreover,the application of functional additives in high-voltage cathodes,lithium-sulfur batteries,and flexible lithiumion batteries is summarized.Finally,future research perspectives are proposed to overcome the unresolved technical hurdles and critical issues in additives of SPEs,such as facile fabrication process,interfacial compatibility,investigation of the working mechanism,and special functionalities.展开更多
Compared with commercial lithium batteries with liquid electrolytes,all-solidstate lithium batteries(ASSLBs)possess the advantages of higher safety,better electrochemical stability,higher energy density,and longer cyc...Compared with commercial lithium batteries with liquid electrolytes,all-solidstate lithium batteries(ASSLBs)possess the advantages of higher safety,better electrochemical stability,higher energy density,and longer cycle life;therefore,ASSLBs have been identified as promising candidates for next-generation safe and stable high-energy-storage devices.The design and fabrication of solid-state electrolytes(SSEs)are vital for the future commercialization of ASSLBs.Among various SSEs,solid polymer composite electrolytes(SPCEs)consisting of inorganic nanofillers and polymer matrix have shown great application prospects in the practice of ASSLBs.The incorporation of inorganic nanofillers into the polymer matrix has been considered as a crucial method to achieve high ionic conductivity for SPCE.In this review,the mechanisms of Li+transport variation caused by incorporating inorganic nanofillers into the polymer matrix are discussed in detail.On the basis of the recent progress,the respective contributions of polymer chains,passive ceramic nanofillers,and active ceramic nanofillers in affecting the Li+transport process of SPCE are reviewed systematically.The inherent relationship between the morphological characteristics of inorganic nanofillers and the ionic conductivity of the resultant SPCE is discussed.Finally,the challenges and future perspectives for developing high-performance SPCE are put forward.This review aims to provide possible strategies for the further improvement of ionic conductivity in inorganic nanoscale filler-reinforced SPCE and highlight their inspiration for future research directions.展开更多
The self-healing solid polymer electrolytes(SHSPEs)can spontaneously eliminate mechanical damages or micro-cracks generated during the assembly or operation of lithium-ion batteries(LIBs),significantly improving cycli...The self-healing solid polymer electrolytes(SHSPEs)can spontaneously eliminate mechanical damages or micro-cracks generated during the assembly or operation of lithium-ion batteries(LIBs),significantly improving cycling performance and extending service life of LIBs.Here,we report a novel cross-linked network SHSPE(PDDP)containing hydrogen bonds and dynamic disulfide bonds with excellent self-healing properties and nonflammability.The combination of hydrogen bonding between urea groups and the metathesis reaction of dynamic disulfide bonds endows PDDP with rapid self-healing capacity at 28°C without external stimulation.Furthermore,the addition of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(EMIMTFSI)improves the ionic conductivity(1.13×10^(−4)S cm^(−1)at 28°C)and non-flammability of PDDP.The assembled Li/PDDP/LiFePO_(4)cell exhibits excellent cycling performance with a discharge capacity of 137 mA h g^(−1)after 300 cycles at 0.2 C.More importantly,the self-healed PDDP can recover almost the same ionic conductivity and cycling performance as the original PDDP.展开更多
Because of its superior safety and excellent processability,solid polymer electrolytes(SPEs)have attracted widespread attention.In lithium based batteries,SPEs have great prospects in replacing leaky and flammable liq...Because of its superior safety and excellent processability,solid polymer electrolytes(SPEs)have attracted widespread attention.In lithium based batteries,SPEs have great prospects in replacing leaky and flammable liquid electrolytes.However,the low ionic conductivity of SPEs cannot meet the requirements of high energy density systems,which is also an important obstacle to its practical application.In this respect,escalating charge carriers(i.e.Li^(+))and Li^(+)transport paths are two major aspects of improving the ionic conductivity of SPEs.This article reviews recent advances from the two perspectives,and the underlying mechanism of these proposed strategies is discussed,including increasing the Li^(+)number and optimizing the Li^(+)transport paths through increasing the types and shortening the distance of Li^(+)transport path.It is hoped that this article can enlighten profound thinking and open up new ways to improve the ionic conductivity of SPEs.展开更多
For solid polymer electrolytes(SPEs),improving their mechanical and electrochemical properties is the key to obtaining batteries with higher safety and higher energy density.Herein,a novel synergistic strategy propose...For solid polymer electrolytes(SPEs),improving their mechanical and electrochemical properties is the key to obtaining batteries with higher safety and higher energy density.Herein,a novel synergistic strategy proposed is preparing a 3D flame-retardant skeleton(3DPA)and adding nano-multifunctional fillers(Li-ILs@ZIF-8).In addition to providing mechanical support for the polyethylene oxide(PEO)matrix,3DPA also has further contributed to the system’s flame retardancy and further improved the safety.Simultaneously,the electrochemical performance is fully guaranteed by rigid Li-ILs@ZIF-8,which provides fast migration channels forLi^(+),reduces the crystallinity of PEO and effectively inhibits lithium dendrites.The limiting oxygen index of the optimal sample(PL3Z/PA)is as high as 20.5%,and the ionic conductivity reaches 2.89×10^(-4) and 0.91×10^(-3) S cm^(-1) at 25 and 55°C,respectively.The assembled Li|PL3Z/PA|Li battery can be cycled stably for more than 1000 h at a current density of 0.1 m A cm^(-2) without short circuit being pierced by lithium dendrites.The specific capacity of the LFP|PL3Z/PA|Li battery was 160.5 m Ah g^(-1) under a current density of 0.5 C,and the capacity retention rate was 90.0%after 300 cycles.展开更多
The solid-state lithium battery is considered as an ideal next-generation energy storage device owing to its high safety,high energy density and low cost.However,the poor ionic conductivity of solid electrolyte and lo...The solid-state lithium battery is considered as an ideal next-generation energy storage device owing to its high safety,high energy density and low cost.However,the poor ionic conductivity of solid electrolyte and low interfacial stability has hindered the application of solid-state lithium battery.Here,a flexible polymer/garnet solid electrolyte is prepared with poly(ethylene oxide),poly(vinylidene fluoride),Li6.75La3 Zr1.75Ta0.25O12,lithium bis(trifluoromethanesulfonyl)imide and oxalate,which exhibits an ionic conductivity of 2.0 ×10^(-4) S cm^(-1) at 55℃,improved mechanical property,wide electrochemical window(4.8 V vs.Li/Li+),enhanced thermal stabilities.Tiny acidic OX was introduced to inhibit the alkalinity reactions between Li6.75La3 Zr1.75Ta0.25O12 and poly(vinylidene fluoride).In order to improve the interfacial stability between cathode and electrolyte,an Al2 O3@LiNi0.5Co0.2Mn0.3O2 based composite cathode framework is also fabricated with poly(ethylene oxide) polymer and lithium salt as additives.The solid-state lithium battery assembled with polymer/garnet solid electrolyte and composite cathode framework demonstrates a high initial discharge capacity of 150.6 mAh g^(-1) and good capacity retention of 86.7% after 80 cycles at 0.2 C and 55℃,which provides a promising choice for achieving the stable electrode/electrolyte interfacial contact in solid-state lithium batteries.展开更多
The novel composite lithium solid polymer electrolytes (SPEs) composed of polyethylene oxide (PEO) matrix and yttrium oxide (Y2O3) nanofillers were prepared by a solution casting method. The crystal morphology o...The novel composite lithium solid polymer electrolytes (SPEs) composed of polyethylene oxide (PEO) matrix and yttrium oxide (Y2O3) nanofillers were prepared by a solution casting method. The crystal morphology of the SPEs was characterized by polarized optical microscope (POM) and wide-angle X-ray diffraction (WAXD). The induced nucleation and steric hindrance effects of Y2O3 nanofillers result in the increased amount as well as decreased size of PEO spherulites which are closely related to the crystallinity of the SPEs. As the Y2O3 contents increase from 0 wt% to 15 wt%, the crystallinity of the SPEs decreases proportionally. The thermal, mechanical and electrical properties of the SPEs were investigated by thermal gravimetric analysis (TGA), dynamic mechanical analysis (DMA) and AC impedance method, respectively. The physical properties including thermal, mechanical and electrical performances, depending remarkably on the polymer-filler interactions between PEO and Y2O3 nanoparticles, are improved by different degrees with the increase of Y2O3 contents. The (PEO)21LiI/10 wt%Y2O3 composite SPE exhibits the optimal room-temperature ionic conductivity of 5.95×10-5 Scm-1, which satisfies the requirements of the conventional electrochromic devices.展开更多
Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performa...Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.展开更多
The increased demand of electronic devices promotes the development of advanced and more efficient energy storage devices, such as batteries. Lithium-ion batteries (LIBs) are the most studied battery systems due to th...The increased demand of electronic devices promotes the development of advanced and more efficient energy storage devices, such as batteries. Lithium-ion batteries (LIBs) are the most studied battery systems due to their high performance. Among the different battery components, the separator allows the control of lithium ion diffusion between the electrodes. To overcome some drawbacks of liquid electrolytes, including safety and environmental issues, solid polymer electrolytes (SPEs) are being developed. In this work, a UV photocurable polyurethane acrylate (PUA) resin has been blended with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) up to 30 wt% LiTFSI content to reach a maximum ionic conductivity of 0.0032 mS/cm at room temperature and 0.09 mS/cm at 100 ℃. Those values allowed applying the developed materials as photocurable SPE in Swagelok type Li/C-LiFePO_(4) half-cells, reaching a battery discharge capacity value of 139 mAh.g^(−1) at C/30 rate. Those results, together with the theoretical studies of the discharge capacity at different C-rates and temperatures for batteries with LiTFSI/PUA SPE demonstrate the suitability of the developed photocurable SPE for LIB applications.展开更多
Poly(ethylene oxide)(PEO)is a classic matrix model for solid polymer electrolyte which can not only dissociate lithium-ions(Li^(+)),but also can conduct Li^(+) through segmental motion in long-range.However,the crysta...Poly(ethylene oxide)(PEO)is a classic matrix model for solid polymer electrolyte which can not only dissociate lithium-ions(Li^(+)),but also can conduct Li^(+) through segmental motion in long-range.However,the crystal aggregation state of PEO restricts the conduction of Li^(+) especially at room temperature.In this work,an amorphous polymer electrolyte with ethylene oxide(EO)and propylene oxide(PO)block structure(B-PEG@DMC)synthesized by the transesterification is firstly obtained,showing an ionic conductivity value of 1.1×10^(5) S/cm at room temperature(25℃).According to the molecular dynamics(MD)simulation,the PO segments would lead to an inconsecutive and hampered conduction of Li^(+),which is not beneficial to the short range conduction of Li^(+).Thus the effect of transformation of aggregation state on the improveme nt of ionic conductivity is not eno ugh,it is n ecessary to further consider the differe nt coupled behaviours of EO and PO segments with Li^(+).In this way,we blend this amorphous polymer(B-PEG@DMC)with PEO to obtain a dual range ionic conductive solid polymer electrolyte(D-SPE)with further improved ionic conductivity promoted by constructing a dual range fast ionic conduction,which eventually shows a further improved ionic conductivity value of 2.3×10^(5) S/cm at room temperature.展开更多
基金supported by the National Natural Science Youth Fund of China(52302247)the Natural Youth Science Foundation of Hunan Province(2022JJ40070)。
文摘Since the advent of the solid-state batteries,employing solid polymer electrolytes(SPEs)to replace routine flammable liquid electrolytes is regarded to be one of the most promising solutions in pursing highenergy-density battery systems.SPEs with superior thermal stability,good processability,and high mechanical modulus obtain increasing attentions.However,SPE-based batteries are not impenetrable due to their decomposition and combustibility under extreme conditions.Researchers believe incorporating appropriate flame-retardant additives/solvents/fragments into SPEs can intrinsically reduce their flammability to solve the battery safety issues.In this review,the recent research progress of incombustible SPEs,with special emphasis on flame-retardant structural design,is summarized.Specifically,a brief introduction of flame-retardant mechanism,evaluation index for safety of SPEs,and a detailed overview of the latest advances on diverse-types SPEs in various battery systems are highlighted.The deep insight into thermal ru naway process,the free-standing incombustible GPEs,and the ratio nal design of pouch cell structures may be the main directions to motivate revolutionary next-generation for safety batteries.
基金This work was supported by the Major Science and Technology Projects of Henan Province(221100230200)the National Key Research and Development Program of China(2020YFB1713500)Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210).
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.
基金financially supported by the National Natural Science Foundation of China(Grant No.22325405,22321002,22279153)Liaoning Revitalization Talents Program(XLYC1807207,XLYC2203134)DICP I202104。
文摘Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.
基金financial support from the National Key R&D Program of China (grant 2022YFB3807700)the National Natural Science Foundation of China (grants 52171225,52102314,52225208,51972285 and U21A20174)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang (grant 2020R01002)。
文摘All-solid-state lithium(Li)metal batteries(ASSLMBs)are considered one of the most promising secondary batteries due to their high theoretical capacity and high safety performance.However,low room-temperature ionic conductivity and poor interfacial stability are two key factors affecting the practical application of ASSLMBs,and our understanding of the mechanisms behind these key problems from microscopic perspective is still limited.In this review,the mechanisms and advanced characterization techniques of ASSLMBs are summarized to correlate the microstructures and properties.Firstly,we summarize the challenges faced by solid polymer electrolytes(SPEs)in ASSLMBs,such as the low roomtemperature ionic conductivity and the poor interfacial stability.Secondly,several typical improvement methods of polymer ASSLMBs are discussed,including composite SPEs,ultra-thin SPEs,SPEs surface modification and Li anode surface modification.Finally,we conclude the characterizations for correlating the microstructures and the properties of SPEs,with emphasis on the use of emerging advanced techniques(e.g.,cryo-transmission electron microscopy)for in-depth analyzing ASSLMBs.The influence of the microstructures on the properties is very important.Until now,it has been difficult for us to understand the microstructures of batteries.However,some recent studies have demonstrated that we have a better understanding of the microstructures of batteries.Then we suggest that in situ characterization,nondestructive characterization and sub-angstrom resolution are the key technologies to help us further understand the batteries'microstructures and promote the development of batteries.And potential investigations to understand the microstructures evolution and the batteries behaviors are also prospected to expect further reasonable theoretical guidance for the design of ASSLMBs with ideal performance.
基金supported by the National Key R&D Program of China (2020YFE0100200)the National Natural Science Foundation of China (Grant Nos.51921002,51927806).
文摘Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for building solid-state lithium batteries due to their excellent flexibility,scalability,and interfacial compatibility with electrodes.However,the low ionic conductivity and poor cyclic stability of SPEs do not meet the requirements for practical applications of lithium batteries.Here,a novel polymer dispersed ionic liquid-based solid polymer electrolyte(PDIL-SPE)is fabricated using the in situ polymerization-induced phase separation(PIPS)method.The as-prepared PDIL-SPE possesses both outstanding ionic conductivity(0.74 mS cm^(-1) at 25℃)and a wide electrochemical window(up to 4.86 V),and the formed unique three-dimensional(3D)co-continuous structure of polymer matrix and ionic liquid in PDIL-SPE can promote the transport of lithium ions.Also,the 3D co-continuous structure of PDIL-SPE effectively accommodates the severe volume expansion for prolonged lithium plating and stripping processes over 1000 h at 0.5 mA cm^(-2) under 25℃.Moreover,the LiFePO_(4)//Li coin cell can work stably over 150 cycles at a 1 C rate under room temperature with a capacity retention of 90.6%from 111.1 to 100.7 mAh g^(-1).The PDIL-SPE composite is a promising material system for enabling the ultrastable operation of solid-state lithium-metal batteries.
基金supported by the National Natural Science Foundation of China(Grant No.52130307).
文摘Electrolytes based on poly(ionic liquid)s(PILs)have attracted great attention in the fields of next-generation solid lithium-ion batteries.However,the low ionic conductivity prevents their practical applications.Herein,we report novel solid electrolytes based on block copolymers composed of PILs and comb-like poly(ethylene glycol)(PEG),which were synthesized via ring-opening metathesis polymerization of 3-(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1-butyl-1H-imidazol-3-ium bis((trifluoromethyl)sulfonyl)amide and poly(ethylene glycol monomethyl ether)bicyclo[2.2.1]hept-5-ene-2-carboxylate.Comb-like PEG acts as plasticizers in block copolymers dominated by PILs to promote the mobility of PILs segments.Effects of the copolymer composition and length of the comb-like PEG chain on ionic conductivity were investigated.The optimized electrolyte delivers the highest ionic conductivity of 1.5×10^(–5)S·cm^(–1)at 30℃,and robust electrochemical stability up to 4.6 V.A solid-state Li/LiFePO4 cell using the optimized electrolyte demonstrates good cycle performance at 0.2 C with high capacity retention of 92%after 70 cycles at 50℃.
基金the support of the Zhejiang Provincial Natural Science Foundation of China (LR20E020002, LD22E020006)the National Natural Science Foundation of China (NSFC) (U20A20253, 21972127, 22279116)。
文摘The rapid development of new energy vehicles and 5G communication technologies has led to higher demands for the safety,energy density,and cycle performance of lithium-ion batteries as power sources.However,the currently used liquid carbonate compounds in commercial lithium-ion battery electrolytes pose potential safety hazards such as leakage,swelling,corrosion,and flammability.Solid electrolytes can be used to mitigate these risks and create a safer lithium battery.Furthermore,high-energy density can be achieved by using solid electrolytes along with high-voltage cathode and metal lithium anode.Two types of solid electrolytes are generally used:inorganic solid electrolytes and polymer solid electrolytes.Inorganic solid electrolytes have high ionic conductivity,electrochemical stability window,and mechanical strength,but suffer from large solid/solid contact resistance between the electrode and electrolyte.Polymer solid electrolytes have good flexibility,processability,and contact interface properties,but low room temperature ionic conductivity,necessitating operation at elevated temperatures.Composite solid electrolytes(CSEs) are a promising alternative because they offer light weight and flexibility,like polymers,as well as the strength and stability of inorganic electrolytes.This paper presents a comprehensive review of recent advances in CSEs to help researchers optimize CSE composition and interactions for practical applications.It covers the development history of solid-state electrolytes,CSE properties with respect to nanofillers,morphology,and polymer types,and also discusses the lithium-ion transport mechanism of the composite electrolyte,and the methods of engineering interfaces with the positive and negative electrodes.Overall,the paper aims to provide an outlook on the potential applications of CSEs in solid-state lithium batteries,and to inspire further research aimed at the development of more systematic optimization strategies for CSEs.
基金The project supported by National Natural Science Foundation of China.
文摘To raise the room temperature ionic conductivity and improve the mechanical strength of a PEO-based polymer electrolyte, a noncrystalline two-component epoxy electrolyte system has been prepared. The diglycidyl ether of polyethylene glycols as precursors of the system were synthesized by a two-step process. The presumed structure of the product was characterized, by ^(13)C, ~1H NMR and IR spectroscopy. It was found that a side-reaction occurred between the secondary hydroxyl group of PEG-chlorohydrin and epichlorohydrin in some degree, resulting in a by- product containing—CH_2Cl side group. By selecting a characteristic signal, which is undistorted by the increase in the length of CH_2 CH_2—O segment, a ~1H NMR approach of determining the equivalent epoxy weight (EEW) was proposed. The method is valid to specimens even though the EEW is as high as 2,000. The examination of the specimens by DSC showed that epoxidation greatly depressed the crystallinity of the PEG's, whereas the T_g was raised.
基金supported by the National Natural Science Foundation of China (Grant Nos.51604089,51874110,22173066,21903058)the Natural Science Foundation of Heilongjiang Province (Grant No.YQ2021B004)Open Project of State Key Laboratory of Urban Water Resource and Environment (Grant No.QA202138)。
文摘Solid polymer electrolytes(SPEs)are one of the most promising alternatives to flammable liquid electrolytes for building safe Li metal batteries.Nevertheless,the poor ionic conductivity at room temperature(RT)and low resistance to Li dendrites seriously hinder the commercialization of SPEs.Herein,we design a bifunctional flame retardant SPE by combining hydroxyapatite(HAP)nanomaterials with Nmethyl pyrrolidone(NMP)in the PVDF-HFP matrix.The addition of HAP generates a hydrogen bond network with the PVDF-HFP matrix and cooperates with NMP to facilitate the dissociation of Li TFSI in the PVDF-HFP matrix.Consequently,the prepared SPE demonstrates superior ionic conductivity at RT,excellent fireproof properties,and strong resistance to Li dendrites.The assembled Li symmetric cell with prepared SPE exhibits a stable cycling performance of over 1200 h at 0.2 m A cm^(-2),and the solid-state LiFePO_4||Li cell shows excellent capacity retention of 85.3%over 600 cycles at 0.5 C.
基金the National Natural Science Foundation of China(Grant No.21875071)the National Natural Science Foundation of China-Hong Kong Research Grant Council(NSFC-RGC)Joint Research Scheme(Grant No.21661162002 and N_HKUST601/16)the Guangzhou Scientific and Technological Planning Project(Grant No.201704030061)。
文摘Solid polymer electrolytes(SPEs), such as polyethylene oxide(PEO), are characteristic of good flexibility and excellent processability, but they suffer from low ionic conductivity and small Li+transference number at ambient temperature. Inorganic solid electrolytes(ISEs), garnet-type Li7La3Zr2O12 and its derivatives(LLZO-based) in particular, possess high ionic conductivity at room temperature, wide electrochemical stability window, large Li+transference number as well as good stability against Li metal anode.Nevertheless, lithium dendrites growth, interfacial contact issue and brittle nature of LLZO-based ceramic electrolytes prevent their practical applications. In response to these shortcomings, LLZO-based/polymer solid composite electrolytes(SCEs), taking complementary advantages of two kinds of electrolytes, and thus simultaneously improving the electrode wettability, ionic conductivity and mechanical strength, have been made to develop high-performance SCEs in recent years. Herein, the intrinsic properties and research progress of LLZO-based/polymer SCEs, including LLZO-based/PEO SCEs(LLZO-based/PEO SCEs with uniform dispersion of LLZO-based fillers and LLZO-based/PEO layered SCEs) and LLZO-based/novel polymers SCEs, are summarized. Besides, comprehensive updates on their applications in solid-state batteries are also presented. Finally, challenges and perspectives of LLZO-based/polymer SCEs for advanced allsolid-state lithium batteries(ASSLBs) are suggested. This review paper aims to provide systematic research progress of LLZO-based/polymer SCEs, to allow for more efficient and target-oriented research on improving LLZO-based/polymer SCEs.
基金supported by the Australian Research Council(ARC)Discovery Projects(DP210103266 and DP1701048343)the Griffith University Ph.D.Scholarships.
文摘Solid polymer electrolytes(SPEs)have become increasingly attractive in solid-state lithium-ion batteries(SSLIBs)in recent years because of their inherent properties of flexibility,processability,and interfacial compatibility.However,the commercialization of SPEs remains challenging for flexible and high-energy-density LIBs.The incorporation of functional additives into SPEs could significantly improve the electrochemical and mechanical properties of SPEs and has created some historical milestones in boosting the development of SPEs.In this study,we review the roles of additives in SPEs,highlighting the working mechanisms and functionalities of the additives.The additives could afford significant advantages in boosting ionic conductivity,increasing ion transference number,improving high-voltage stability,enhancing mechanical strength,inhibiting lithium dendrite,and reducing flammability.Moreover,the application of functional additives in high-voltage cathodes,lithium-sulfur batteries,and flexible lithiumion batteries is summarized.Finally,future research perspectives are proposed to overcome the unresolved technical hurdles and critical issues in additives of SPEs,such as facile fabrication process,interfacial compatibility,investigation of the working mechanism,and special functionalities.
基金the National Natural Science Foundation of China(Grant No.21673051)the Department of Science and Technology of Guangdong Province,China(No.2019A050510043).
文摘Compared with commercial lithium batteries with liquid electrolytes,all-solidstate lithium batteries(ASSLBs)possess the advantages of higher safety,better electrochemical stability,higher energy density,and longer cycle life;therefore,ASSLBs have been identified as promising candidates for next-generation safe and stable high-energy-storage devices.The design and fabrication of solid-state electrolytes(SSEs)are vital for the future commercialization of ASSLBs.Among various SSEs,solid polymer composite electrolytes(SPCEs)consisting of inorganic nanofillers and polymer matrix have shown great application prospects in the practice of ASSLBs.The incorporation of inorganic nanofillers into the polymer matrix has been considered as a crucial method to achieve high ionic conductivity for SPCE.In this review,the mechanisms of Li+transport variation caused by incorporating inorganic nanofillers into the polymer matrix are discussed in detail.On the basis of the recent progress,the respective contributions of polymer chains,passive ceramic nanofillers,and active ceramic nanofillers in affecting the Li+transport process of SPCE are reviewed systematically.The inherent relationship between the morphological characteristics of inorganic nanofillers and the ionic conductivity of the resultant SPCE is discussed.Finally,the challenges and future perspectives for developing high-performance SPCE are put forward.This review aims to provide possible strategies for the further improvement of ionic conductivity in inorganic nanoscale filler-reinforced SPCE and highlight their inspiration for future research directions.
基金supported by R&D Program of Power Batteries with Low Temperature and High Energy,Science and Technology Bureau of Changchun(19SS013)Key Subject Construction of Physical Chemistry of Northeast Normal University+1 种基金the Fundamental Research Funds for the Central Universities(2412020FZ007,2412020FZ008)National Natural Science Foundation of China(22102020)
文摘The self-healing solid polymer electrolytes(SHSPEs)can spontaneously eliminate mechanical damages or micro-cracks generated during the assembly or operation of lithium-ion batteries(LIBs),significantly improving cycling performance and extending service life of LIBs.Here,we report a novel cross-linked network SHSPE(PDDP)containing hydrogen bonds and dynamic disulfide bonds with excellent self-healing properties and nonflammability.The combination of hydrogen bonding between urea groups and the metathesis reaction of dynamic disulfide bonds endows PDDP with rapid self-healing capacity at 28°C without external stimulation.Furthermore,the addition of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(EMIMTFSI)improves the ionic conductivity(1.13×10^(−4)S cm^(−1)at 28°C)and non-flammability of PDDP.The assembled Li/PDDP/LiFePO_(4)cell exhibits excellent cycling performance with a discharge capacity of 137 mA h g^(−1)after 300 cycles at 0.2 C.More importantly,the self-healed PDDP can recover almost the same ionic conductivity and cycling performance as the original PDDP.
基金supported by the National Natural Science Foundation of China(51872196)the Natural Science Foundation of Tianjin,China(17JCJQJC44100)the National Postdoctoral Program for Innovative Talents,China(BX20190232)。
文摘Because of its superior safety and excellent processability,solid polymer electrolytes(SPEs)have attracted widespread attention.In lithium based batteries,SPEs have great prospects in replacing leaky and flammable liquid electrolytes.However,the low ionic conductivity of SPEs cannot meet the requirements of high energy density systems,which is also an important obstacle to its practical application.In this respect,escalating charge carriers(i.e.Li^(+))and Li^(+)transport paths are two major aspects of improving the ionic conductivity of SPEs.This article reviews recent advances from the two perspectives,and the underlying mechanism of these proposed strategies is discussed,including increasing the Li^(+)number and optimizing the Li^(+)transport paths through increasing the types and shortening the distance of Li^(+)transport path.It is hoped that this article can enlighten profound thinking and open up new ways to improve the ionic conductivity of SPEs.
基金supported by the National Key Research and Development Program of China(Grant No.2017YFA0204600)the National Natural Science Foundation of China(Grant No.5210021666)the Key R&D and Promotion Projects of Henan Province(Grant No.212102310016)。
文摘For solid polymer electrolytes(SPEs),improving their mechanical and electrochemical properties is the key to obtaining batteries with higher safety and higher energy density.Herein,a novel synergistic strategy proposed is preparing a 3D flame-retardant skeleton(3DPA)and adding nano-multifunctional fillers(Li-ILs@ZIF-8).In addition to providing mechanical support for the polyethylene oxide(PEO)matrix,3DPA also has further contributed to the system’s flame retardancy and further improved the safety.Simultaneously,the electrochemical performance is fully guaranteed by rigid Li-ILs@ZIF-8,which provides fast migration channels forLi^(+),reduces the crystallinity of PEO and effectively inhibits lithium dendrites.The limiting oxygen index of the optimal sample(PL3Z/PA)is as high as 20.5%,and the ionic conductivity reaches 2.89×10^(-4) and 0.91×10^(-3) S cm^(-1) at 25 and 55°C,respectively.The assembled Li|PL3Z/PA|Li battery can be cycled stably for more than 1000 h at a current density of 0.1 m A cm^(-2) without short circuit being pierced by lithium dendrites.The specific capacity of the LFP|PL3Z/PA|Li battery was 160.5 m Ah g^(-1) under a current density of 0.5 C,and the capacity retention rate was 90.0%after 300 cycles.
基金Financial supports from the National Natural Science Foundation of China (51575030, 51532002 and 51872027)Beijing Natural Science Foundation (L172023)National Basic Research Program of China (2017YFE0113500)。
文摘The solid-state lithium battery is considered as an ideal next-generation energy storage device owing to its high safety,high energy density and low cost.However,the poor ionic conductivity of solid electrolyte and low interfacial stability has hindered the application of solid-state lithium battery.Here,a flexible polymer/garnet solid electrolyte is prepared with poly(ethylene oxide),poly(vinylidene fluoride),Li6.75La3 Zr1.75Ta0.25O12,lithium bis(trifluoromethanesulfonyl)imide and oxalate,which exhibits an ionic conductivity of 2.0 ×10^(-4) S cm^(-1) at 55℃,improved mechanical property,wide electrochemical window(4.8 V vs.Li/Li+),enhanced thermal stabilities.Tiny acidic OX was introduced to inhibit the alkalinity reactions between Li6.75La3 Zr1.75Ta0.25O12 and poly(vinylidene fluoride).In order to improve the interfacial stability between cathode and electrolyte,an Al2 O3@LiNi0.5Co0.2Mn0.3O2 based composite cathode framework is also fabricated with poly(ethylene oxide) polymer and lithium salt as additives.The solid-state lithium battery assembled with polymer/garnet solid electrolyte and composite cathode framework demonstrates a high initial discharge capacity of 150.6 mAh g^(-1) and good capacity retention of 86.7% after 80 cycles at 0.2 C and 55℃,which provides a promising choice for achieving the stable electrode/electrolyte interfacial contact in solid-state lithium batteries.
基金Funded by the National Natural Science Foundation of China (No. 51003082)the Key Project of Science and Technology Research of Ministry of Education (No. 208089)+2 种基金the Educational Commission of Hubei Province (No.Q20101606)the Young Outstanding Talent Foundation of Hubei Province (No.2008CDB261)the Natural Science Foundation of Hubei Province (No. 2007ABA075)
文摘The novel composite lithium solid polymer electrolytes (SPEs) composed of polyethylene oxide (PEO) matrix and yttrium oxide (Y2O3) nanofillers were prepared by a solution casting method. The crystal morphology of the SPEs was characterized by polarized optical microscope (POM) and wide-angle X-ray diffraction (WAXD). The induced nucleation and steric hindrance effects of Y2O3 nanofillers result in the increased amount as well as decreased size of PEO spherulites which are closely related to the crystallinity of the SPEs. As the Y2O3 contents increase from 0 wt% to 15 wt%, the crystallinity of the SPEs decreases proportionally. The thermal, mechanical and electrical properties of the SPEs were investigated by thermal gravimetric analysis (TGA), dynamic mechanical analysis (DMA) and AC impedance method, respectively. The physical properties including thermal, mechanical and electrical performances, depending remarkably on the polymer-filler interactions between PEO and Y2O3 nanoparticles, are improved by different degrees with the increase of Y2O3 contents. The (PEO)21LiI/10 wt%Y2O3 composite SPE exhibits the optimal room-temperature ionic conductivity of 5.95×10-5 Scm-1, which satisfies the requirements of the conventional electrochromic devices.
基金support of the Fundamental Research Funds for the Central Universities(No.2022CDJQY-004)the Fund for Innovative Research Groups of Natural Science Foundation of Hebei Province(No.A2020202002).
文摘Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.
基金Work supported by the Portuguese national funds(PIDDAC),through the Portuguese Foundation for Science and Technology(FCT)and FCT/MCTES:projects UID/FIS/04650/2020.UID/QUI/0686/2020,UID/CTM/50025/2020,UIDB/05549/2020,PTDC/FIS-MAC/28157/2017Grants SFRH/BD/140842/2018(J.C.B.),CEECIND/00833/2017(R.G.)and SFRH/BPD/112547/2015(C.M.C.).Financial support from the Basque Government Industry Departments under the ELKARTEK and HAZITEK programs is also acknowledged.
文摘The increased demand of electronic devices promotes the development of advanced and more efficient energy storage devices, such as batteries. Lithium-ion batteries (LIBs) are the most studied battery systems due to their high performance. Among the different battery components, the separator allows the control of lithium ion diffusion between the electrodes. To overcome some drawbacks of liquid electrolytes, including safety and environmental issues, solid polymer electrolytes (SPEs) are being developed. In this work, a UV photocurable polyurethane acrylate (PUA) resin has been blended with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) up to 30 wt% LiTFSI content to reach a maximum ionic conductivity of 0.0032 mS/cm at room temperature and 0.09 mS/cm at 100 ℃. Those values allowed applying the developed materials as photocurable SPE in Swagelok type Li/C-LiFePO_(4) half-cells, reaching a battery discharge capacity value of 139 mAh.g^(−1) at C/30 rate. Those results, together with the theoretical studies of the discharge capacity at different C-rates and temperatures for batteries with LiTFSI/PUA SPE demonstrate the suitability of the developed photocurable SPE for LIB applications.
基金support from the National Natural Science Foundation of China[22021001,21875195]the Fundamental Research Funds for the Central Universities[20720190040]the Key Project of Science and Technology of Xiamen[3502Z20201013]。
文摘Poly(ethylene oxide)(PEO)is a classic matrix model for solid polymer electrolyte which can not only dissociate lithium-ions(Li^(+)),but also can conduct Li^(+) through segmental motion in long-range.However,the crystal aggregation state of PEO restricts the conduction of Li^(+) especially at room temperature.In this work,an amorphous polymer electrolyte with ethylene oxide(EO)and propylene oxide(PO)block structure(B-PEG@DMC)synthesized by the transesterification is firstly obtained,showing an ionic conductivity value of 1.1×10^(5) S/cm at room temperature(25℃).According to the molecular dynamics(MD)simulation,the PO segments would lead to an inconsecutive and hampered conduction of Li^(+),which is not beneficial to the short range conduction of Li^(+).Thus the effect of transformation of aggregation state on the improveme nt of ionic conductivity is not eno ugh,it is n ecessary to further consider the differe nt coupled behaviours of EO and PO segments with Li^(+).In this way,we blend this amorphous polymer(B-PEG@DMC)with PEO to obtain a dual range ionic conductive solid polymer electrolyte(D-SPE)with further improved ionic conductivity promoted by constructing a dual range fast ionic conduction,which eventually shows a further improved ionic conductivity value of 2.3×10^(5) S/cm at room temperature.