Inhomogeneous lithium-ion(Li^(+))deposition is one of the most crucial problems,which severely deteriorates the performance of solid-state lithium metal batteries(LMBs).Herein,we discovered that covalent organic frame...Inhomogeneous lithium-ion(Li^(+))deposition is one of the most crucial problems,which severely deteriorates the performance of solid-state lithium metal batteries(LMBs).Herein,we discovered that covalent organic framework(COF-1)with periodically arranged boron-oxygen dipole lithiophilic sites could directionally guide Li^(+)even deposition in asymmetric solid polymer electrolytes.This in situ prepared 3D cross-linked network Poly(ACMO-MBA)hybrid electrolyte simultaneously delivers outstanding ionic conductivity(1.02×10^(-3)S cm^(-1)at 30°C)and excellent mechanical property(3.5 MPa).The defined nanosized channel in COF-1 selectively conducts Li^(+)increasing Li^(+)transference number to 0.67.Besides,The COF-1 layer and Poly(ACMO-MBA)also participate in forming a boron-rich and nitrogen-rich solid electrolyte interface to further improve the interfacial stability.The Li‖Li symmetric cell exhibits remarkable cyclic stability over 1000 h.The Li‖NCM523 full cell also delivers an outstanding lifespan over 400 cycles.Moreover,the Li‖LiFePO_(4)full cell stably cycles with a capacity retention of 85%after 500 cycles.the Li‖LiFePO_(4)pouch full exhibits excellent safety performance under pierced and cut conditions.This work thereby further broadens and complements the application of COF materials in polymer electrolyte for dendrite-free and high-energy-density solid-state LMBs.展开更多
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
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
Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n(LiClO4)∶n(LiNO3)∶n(LiBr)=1.6∶3.8∶1.0 was prepared. The poly(lithium acrylate-acrylonitrile)/LiClO4-...Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n(LiClO4)∶n(LiNO3)∶n(LiBr)=1.6∶3.8∶1.0 was prepared. The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes were prepared with poly(lithium acrylate-acrylonitrile) and (LiClO4-LiNO3-LiBr) eutectic salts. The effect of LiClO4-LiNO3-LiBr eutectic salts content on the conductivity of solid polymer electrolytes was studied by alternating current impedance method, and the structures of eutectic salts and solid polymer electrolytes were characterized by differential thermal analysis, infrared spectroscopy and X-ray diffractometry. The results show that the room temperature conductivity of LiClO4-LiNO3-LiBr eutectic salts reaches (3.11×10-4 S·cm-1.) The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes possess the highest room temperature conductivity at 70% LiClO4-LiNO3-LiBr eutectic salts content, and exhibit lower glass transition temperature of 75 ℃ compared with that of poly(lithium acrylate-acrylonitrile) of 105 ℃. A complex may be formed in the solid polymer electrolytes from the differential thermal analysis and infrared spectroscopy analysis. X-ray diffraction results show that the poly(lithium acrylate-acrylonitrile) can suppress the crystallization of eutectic salts in this system.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
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
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
In this paper, the effect of hydrogen reduction of silver ions on the performance and structure of new solid polymer electrolyte polyetherimide (PEI)/Pebax2533 (Polynylonl2/tetramethylene oxide block copolymer, PA1...In this paper, the effect of hydrogen reduction of silver ions on the performance and structure of new solid polymer electrolyte polyetherimide (PEI)/Pebax2533 (Polynylonl2/tetramethylene oxide block copolymer, PA12-PTMO)/AgBF4 composite membranes is investigated. For PEI/Pebax2533/AgBF4 composite membranesprepared with dillerent AgBF4 concentration, the permeances of propylene and ethylene increase with the increase of AgBF4 concentration due to the carrier-facilitated transport, resulting in a high selectivity. But for propyl- ene/propane mixture, the mixed-gas selectivity is lower than its ideal selectivity. The hydrogen reduction strongly influences the membrane performance, which causes the decrease of propylene permeance and the increase of pro-pane permeance. With the increase of hydrogen reduction time, the membranes show a clearly color change from white to brown, yielding a great selectivity loss. The data of X-ray diffraction and FT-IR prove that silver ions are reduced to Ago after hydrogen reduction, and aggregated on the surface of PEI/Pebax2533/AgBF4 composite mem- branes.展开更多
A new solid polymer electrolyte PEO20-LiTf-Urea1.5 was prepared by solution casting technique. The energy of frontier orbitals for the components of the electrolyte was predicted by quantum chemistry calculations, and...A new solid polymer electrolyte PEO20-LiTf-Urea1.5 was prepared by solution casting technique. The energy of frontier orbitals for the components of the electrolyte was predicted by quantum chemistry calculations, and TG stability and electrochemical features were measured. Urea exhibited a lower HOMO energy than PEO, implying its enhanced stability against electrochemical oxidation. Experimentally addition of urea increases the ionic conductivity, which guarantees conductivity requirement for lithium ion batteries. It also results in significant improved electrochemical stability with good thermal stability. Favorable lithium stripping/plating performance is yielded, and it confirms the good stability of the solid electrolyte interphase for the PEO20-LiTf-Urea1.5 system.展开更多
A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses the...A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.展开更多
Solid polymer electrolytes(SPEs)are promising substitutes for current flammable liquid electrolytes to achieve high-safety and high-energy-density lithium metal batteries.Polyethylene oxide(PEO)based solid polymer ele...Solid polymer electrolytes(SPEs)are promising substitutes for current flammable liquid electrolytes to achieve high-safety and high-energy-density lithium metal batteries.Polyethylene oxide(PEO)based solid polymer electrolytes have attracted increasing attention because of their excellent flexibility,manufacturability,light weight,and low-cost processing,while they often suffer from low ionic con-ductivity at room temperature,low lithium transference number and unsatisfactory interfacial resis-tance,which largely restrain their practical application.Herein,two-dimensional holey silica nanosheets(2D-HSN)as the fillers,together with LiNO_(3) as the electrolyte additive,are introduced in a PEO/poly(-vinylidene fiuoride-co-hexafluoropropylene)(PVDF-HFP)blended polymer matrix to obtain a SPE.The incorporation of HSN filler creates supplementary channels for lithium ion migration and lowers the crystallinity of the polymer,thereby facilitating the movement of lithium ions.The HSN-based SPE demonstrates higher ionic conductivity up to 3.7 x 10-4 S cm-1 at 30℃,larger Li+transference number close to 0.34,and more stable lithium plating/stripping than that without the fillers,and HSN can promote the formation of more stable solid electrolyte interphase(SEI)layer.The as-assembled LiFePO4||Li batteries deliver a high specific capacity of 159 mA h g-1 with the capacity retention of 95.5%after 200 cycles at 30℃,as well as superior rate performance and cycling stability compared to that using the blank SPE.展开更多
In order to enhance the ionic conductivity of solid polymer electrolytes(SPEs)and their structural rigidity against lithium dendrite during lithium-ion battery(LIB)cycling,we propose porous garnet Li6.4La3Zr2Al0.2O12(...In order to enhance the ionic conductivity of solid polymer electrolytes(SPEs)and their structural rigidity against lithium dendrite during lithium-ion battery(LIB)cycling,we propose porous garnet Li6.4La3Zr2Al0.2O12(LLZO),as the filler to SPEs.The porous LLZO with interlinked grains was synthesized via a resol-assisted cationic coordinative co-assembly approach.The porous structure of LLZO with high specific surface area facilitates the interaction between polymer and filler and provides sufficient entrance for Li^(+)migration into the LLZO phase.Furthermore,the interconnection of LLZO grains forms continuous inorganic pathways for fast Li^(+)migration,which avoid the multiple diffusion for Li^(+)in interface.As a result,the SPEs with porous LLZO(SPE-PL)show a high ionic conductive of 0.73 mS·cm^(-1) at 30℃ and lithium-ion transference number of 0.40.The porous LLZO with uniformly dispersed pores also acts as an ion distributor to regulate ionic flux.The lithium-symmetrical batteries assembled with SPE-PL show a highly stable Li plating/stripping cycling for nearly 3000 h at 0.1 mA·cm^(-2).The corresponding Li/LiFePO_(4) batteries also exhibit excellent cyclic performance with capacity retention of 75%after nearly 500 cycles.This work brings new insights into the design of conductive fillers and the optimization of SPEs.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)based all-solid-state batteries(ASSBs)have attracted extensive attention as a promising candidate for next-generation energy storage systems.Typical ASSBs require high fabrication press...Solid polymer electrolytes(SPEs)based all-solid-state batteries(ASSBs)have attracted extensive attention as a promising candidate for next-generation energy storage systems.Typical ASSBs require high fabrication pressure to achieve high areal capacity,under which,however,SPEs struggle and risk damage or failure due to their low mechanical strength.There is also a lack of study on complex stress and strain SPEs experience during ASSB cell assembly processes.Here,ceramic solid electrolytes are selected as interlayers to address the stress-strain conditions during assembling.As a result,high areal capacity ASSBs with a LiCoO2 loading of 12 mg·cm^(-2) were assembled with SPE-based composite electrolytes.Around 200 cycles were carried out for these cells at a current density of 1 mA·cm^(-2) under room temperature.The capacity decay of the battery at 200 cycles is observed to be as low as 0.06% per cycle.This work identifies a critical issue for application of SPEs in ASSBs and provides a potential strategy for the design of SPE-based ASSBs with high specific energy and long cycle life.展开更多
Integrating lithium metal anodes with polymer electrolytes is a promising technology for the next generation high-energy-density rechargeable batteries.As the progress is often hindered by the dendrite growth upon cyc...Integrating lithium metal anodes with polymer electrolytes is a promising technology for the next generation high-energy-density rechargeable batteries.As the progress is often hindered by the dendrite growth upon cycling,quantifying three-dimensional(3D)microstructures of dendrites in polymer electrolytes is essential to better understanding of dendrite formation for the development of mitigation strategies.Techniques for 3D quantification and visualization of dendrites,especially those with low Li contents,are rather limited.This study reports quantitative measurements of the spatial distribution of Li dendrites grown in solid polymer electrolytes using 3D tomographic neutron depth profiling(NDP)with improved spatial resolution,compositional range,and data presentation.Data reveal heterogeneous distribution of Li over length scales from tens nanometers to centimeters.While most dendrites grow from the plating toward the stripping electrode with dwindling Li quantities,dendrites apparently grown from the Li-stripping electrode are also observed.The discovery is only possibly due to the unique combination of the high specificity and high sensitivity of the neutron activation analysis of Li isotope.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
In comparison with lithium-ion batteries(LIBs)with liquid electrolytes,all-solid-state lithium batteries(ASSLBs)have been considered as promising systems for future energy storage due to their safety and high energy d...In comparison with lithium-ion batteries(LIBs)with liquid electrolytes,all-solid-state lithium batteries(ASSLBs)have been considered as promising systems for future energy storage due to their safety and high energy density.As the pivotal component used in ASSLBs,composite solid polymer electrolytes(CSPEs),derived from the incorporation of inorganic fillers into solid polymer electrolytes(SPEs),exhibit higher ionic conductivity,better mechanical strength,and superior thermal/electrochemical stability compared to the single-component SPEs,which can significantly promote the electrochemical performance of ASSLBs.Herein,the recent advances of CSPEs applied in ASSLBs are presented.The effects of the category,morphology and concentration of inorganic fillers on the ionic conductivity,mechanical strength,electrochemical window,interfacial stability and possible Li+transfer mechanism of CSPEs will be systematically discussed.Finally,the challenges and perspectives are proposed for the future development of high-performance CSPEs and ASSLBs.展开更多
Nano Research volume 13,pages2259–2267(2020)Cite this article 277 Accesses 1 Altmetric Metrics details Abstract The incorporation of inorganic fillers into poly(ethyleneoxide)(PEO)-based solid polymer electrolytes(SP...Nano Research volume 13,pages2259–2267(2020)Cite this article 277 Accesses 1 Altmetric Metrics details Abstract The incorporation of inorganic fillers into poly(ethyleneoxide)(PEO)-based solid polymer electrolytes(SPEs)is well known as a low-cost and effective method to improve their mechanical and electrochemical properties.Porous zeolitic imidazolate framework-8(ZIF-8)is firstly used as the filler for PEO-based SPEs in this work.Due to the introduction of ZIF-8,an ionic conductivity of 2.2×10^−5 S/cm(30℃)is achieved for the composite SPE,which is one order of magnitude higher than that of the pure PEO.ZIF-8 also accounts for the broader electrochemical stability window and lithium ion transference number(0.36 at 60℃)of the composite SPE.Moreover,the improved mechanism of ZIF-8 to the composite SPE is investigated by zeta potential and Fourier transform infrared spectrograph characterizations.The stability at the composite SPE/lithium interface is greatly enhanced.The LiFePO4||Li cells using the composite SPE exhibit high capacity and excellent cycling performance at 60℃,i.e.,85%capacity retention with 111 mA·h/g capacity retained after 350 cycles at 0.5 C.In comparison,the cells using the pure PEO show fast capacity decay to 74 mA·h/g maintaining only 68 capacity.These results indicate that the PEO-based SPEs with ZIF-8 are of great promise for the application in solid-state lithium metal batteries.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
基金financially supported by the National Natural Science Foundation of China(No.52273081,No.22278329)Young Talent Support Plan of Xi’an Jiaotong University+2 种基金Natural Science Basic Research Program of Shaanxi(No.2022TD-27,No.2020-JC-09)the financial support from Swedish Research Council Grant(2021-05839)the“Young Talent Support Plan”of Xi’an Jiaotong University
文摘Inhomogeneous lithium-ion(Li^(+))deposition is one of the most crucial problems,which severely deteriorates the performance of solid-state lithium metal batteries(LMBs).Herein,we discovered that covalent organic framework(COF-1)with periodically arranged boron-oxygen dipole lithiophilic sites could directionally guide Li^(+)even deposition in asymmetric solid polymer electrolytes.This in situ prepared 3D cross-linked network Poly(ACMO-MBA)hybrid electrolyte simultaneously delivers outstanding ionic conductivity(1.02×10^(-3)S cm^(-1)at 30°C)and excellent mechanical property(3.5 MPa).The defined nanosized channel in COF-1 selectively conducts Li^(+)increasing Li^(+)transference number to 0.67.Besides,The COF-1 layer and Poly(ACMO-MBA)also participate in forming a boron-rich and nitrogen-rich solid electrolyte interface to further improve the interfacial stability.The Li‖Li symmetric cell exhibits remarkable cyclic stability over 1000 h.The Li‖NCM523 full cell also delivers an outstanding lifespan over 400 cycles.Moreover,the Li‖LiFePO_(4)full cell stably cycles with a capacity retention of 85%after 500 cycles.the Li‖LiFePO_(4)pouch full exhibits excellent safety performance under pierced and cut conditions.This work thereby further broadens and complements the application of COF materials in polymer electrolyte for dendrite-free and high-energy-density solid-state LMBs.
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.
文摘Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n(LiClO4)∶n(LiNO3)∶n(LiBr)=1.6∶3.8∶1.0 was prepared. The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes were prepared with poly(lithium acrylate-acrylonitrile) and (LiClO4-LiNO3-LiBr) eutectic salts. The effect of LiClO4-LiNO3-LiBr eutectic salts content on the conductivity of solid polymer electrolytes was studied by alternating current impedance method, and the structures of eutectic salts and solid polymer electrolytes were characterized by differential thermal analysis, infrared spectroscopy and X-ray diffractometry. The results show that the room temperature conductivity of LiClO4-LiNO3-LiBr eutectic salts reaches (3.11×10-4 S·cm-1.) The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes possess the highest room temperature conductivity at 70% LiClO4-LiNO3-LiBr eutectic salts content, and exhibit lower glass transition temperature of 75 ℃ compared with that of poly(lithium acrylate-acrylonitrile) of 105 ℃. A complex may be formed in the solid polymer electrolytes from the differential thermal analysis and infrared spectroscopy analysis. X-ray diffraction results show that the poly(lithium acrylate-acrylonitrile) can suppress the crystallization of eutectic salts in this system.
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.
基金Supported by the National Natural Science Foundation of China (20776137) and the National High Technology Research and Develooment Prozram of China (2008AA06Z325).
文摘In this paper, the effect of hydrogen reduction of silver ions on the performance and structure of new solid polymer electrolyte polyetherimide (PEI)/Pebax2533 (Polynylonl2/tetramethylene oxide block copolymer, PA12-PTMO)/AgBF4 composite membranes is investigated. For PEI/Pebax2533/AgBF4 composite membranesprepared with dillerent AgBF4 concentration, the permeances of propylene and ethylene increase with the increase of AgBF4 concentration due to the carrier-facilitated transport, resulting in a high selectivity. But for propyl- ene/propane mixture, the mixed-gas selectivity is lower than its ideal selectivity. The hydrogen reduction strongly influences the membrane performance, which causes the decrease of propylene permeance and the increase of pro-pane permeance. With the increase of hydrogen reduction time, the membranes show a clearly color change from white to brown, yielding a great selectivity loss. The data of X-ray diffraction and FT-IR prove that silver ions are reduced to Ago after hydrogen reduction, and aggregated on the surface of PEI/Pebax2533/AgBF4 composite mem- branes.
基金Supported by the National High Technology Research and Development Program of China(No.2008AA11A102)
文摘A new solid polymer electrolyte PEO20-LiTf-Urea1.5 was prepared by solution casting technique. The energy of frontier orbitals for the components of the electrolyte was predicted by quantum chemistry calculations, and TG stability and electrochemical features were measured. Urea exhibited a lower HOMO energy than PEO, implying its enhanced stability against electrochemical oxidation. Experimentally addition of urea increases the ionic conductivity, which guarantees conductivity requirement for lithium ion batteries. It also results in significant improved electrochemical stability with good thermal stability. Favorable lithium stripping/plating performance is yielded, and it confirms the good stability of the solid electrolyte interphase for the PEO20-LiTf-Urea1.5 system.
基金supported by a National Research Foundation of Korea(NRF)Grant funded by the Ministry of Science and ICT(2021R1A2C1014294,2022R1A2C3003319)the BK21 FOUR(Fostering Outstanding Universities for Research)through the National Research Foundation(NRF)of Korea.
文摘A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.
基金supported by National Natural Science Foundation of China(grant Nos.52062004 and 51972070)Guizhou Provincial High Level Innovative Talents Project(grant No.QKHPTRC-GCC[2022]013-1)+1 种基金Guizhou Provincial Science and Technology Projects(grant Nos.QKHJC[2020]1Z042,QKHJC[2020]1Y230 and QKHZC[2021]YB317)Cultivation Project of Guizhou University(grant No.GDPY[2019]01).
文摘Solid polymer electrolytes(SPEs)are promising substitutes for current flammable liquid electrolytes to achieve high-safety and high-energy-density lithium metal batteries.Polyethylene oxide(PEO)based solid polymer electrolytes have attracted increasing attention because of their excellent flexibility,manufacturability,light weight,and low-cost processing,while they often suffer from low ionic con-ductivity at room temperature,low lithium transference number and unsatisfactory interfacial resis-tance,which largely restrain their practical application.Herein,two-dimensional holey silica nanosheets(2D-HSN)as the fillers,together with LiNO_(3) as the electrolyte additive,are introduced in a PEO/poly(-vinylidene fiuoride-co-hexafluoropropylene)(PVDF-HFP)blended polymer matrix to obtain a SPE.The incorporation of HSN filler creates supplementary channels for lithium ion migration and lowers the crystallinity of the polymer,thereby facilitating the movement of lithium ions.The HSN-based SPE demonstrates higher ionic conductivity up to 3.7 x 10-4 S cm-1 at 30℃,larger Li+transference number close to 0.34,and more stable lithium plating/stripping than that without the fillers,and HSN can promote the formation of more stable solid electrolyte interphase(SEI)layer.The as-assembled LiFePO4||Li batteries deliver a high specific capacity of 159 mA h g-1 with the capacity retention of 95.5%after 200 cycles at 30℃,as well as superior rate performance and cycling stability compared to that using the blank SPE.
基金supported by the National Natural Science Foundation of China(No.21805147)Natural Science Foundation of Shandong Province(No.ZR202211240080).
文摘In order to enhance the ionic conductivity of solid polymer electrolytes(SPEs)and their structural rigidity against lithium dendrite during lithium-ion battery(LIB)cycling,we propose porous garnet Li6.4La3Zr2Al0.2O12(LLZO),as the filler to SPEs.The porous LLZO with interlinked grains was synthesized via a resol-assisted cationic coordinative co-assembly approach.The porous structure of LLZO with high specific surface area facilitates the interaction between polymer and filler and provides sufficient entrance for Li^(+)migration into the LLZO phase.Furthermore,the interconnection of LLZO grains forms continuous inorganic pathways for fast Li^(+)migration,which avoid the multiple diffusion for Li^(+)in interface.As a result,the SPEs with porous LLZO(SPE-PL)show a high ionic conductive of 0.73 mS·cm^(-1) at 30℃ and lithium-ion transference number of 0.40.The porous LLZO with uniformly dispersed pores also acts as an ion distributor to regulate ionic flux.The lithium-symmetrical batteries assembled with SPE-PL show a highly stable Li plating/stripping cycling for nearly 3000 h at 0.1 mA·cm^(-2).The corresponding Li/LiFePO_(4) batteries also exhibit excellent cyclic performance with capacity retention of 75%after nearly 500 cycles.This work brings new insights into the design of conductive fillers and the optimization of SPEs.
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the National Key R&D Program of China(No.2021YFB3800300)Science and Technology Commission of Shanghai Municipality(No.23DZ1200800)China Postdoctoral Science Foundation(Nos.BX20220199 and 2023M732208).
文摘Solid polymer electrolytes(SPEs)based all-solid-state batteries(ASSBs)have attracted extensive attention as a promising candidate for next-generation energy storage systems.Typical ASSBs require high fabrication pressure to achieve high areal capacity,under which,however,SPEs struggle and risk damage or failure due to their low mechanical strength.There is also a lack of study on complex stress and strain SPEs experience during ASSB cell assembly processes.Here,ceramic solid electrolytes are selected as interlayers to address the stress-strain conditions during assembling.As a result,high areal capacity ASSBs with a LiCoO2 loading of 12 mg·cm^(-2) were assembled with SPE-based composite electrolytes.Around 200 cycles were carried out for these cells at a current density of 1 mA·cm^(-2) under room temperature.The capacity decay of the battery at 200 cycles is observed to be as low as 0.06% per cycle.This work identifies a critical issue for application of SPEs in ASSBs and provides a potential strategy for the design of SPE-based ASSBs with high specific energy and long cycle life.
基金supported by the Guangdong Basic and Applied Basic Research Foundation(Grant No.2019A1515110398)National Natural Science Foundation of China(Grant No.12105197)H.Wang acknowledges the support of the National Institute of Standards and Technology through award 70NANB12H238.
文摘Integrating lithium metal anodes with polymer electrolytes is a promising technology for the next generation high-energy-density rechargeable batteries.As the progress is often hindered by the dendrite growth upon cycling,quantifying three-dimensional(3D)microstructures of dendrites in polymer electrolytes is essential to better understanding of dendrite formation for the development of mitigation strategies.Techniques for 3D quantification and visualization of dendrites,especially those with low Li contents,are rather limited.This study reports quantitative measurements of the spatial distribution of Li dendrites grown in solid polymer electrolytes using 3D tomographic neutron depth profiling(NDP)with improved spatial resolution,compositional range,and data presentation.Data reveal heterogeneous distribution of Li over length scales from tens nanometers to centimeters.While most dendrites grow from the plating toward the stripping electrode with dwindling Li quantities,dendrites apparently grown from the Li-stripping electrode are also observed.The discovery is only possibly due to the unique combination of the high specificity and high sensitivity of the neutron activation analysis of Li isotope.
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 Innovative and Entrepreneurial Talent Plan(Jiangsu Province,China)。
文摘In comparison with lithium-ion batteries(LIBs)with liquid electrolytes,all-solid-state lithium batteries(ASSLBs)have been considered as promising systems for future energy storage due to their safety and high energy density.As the pivotal component used in ASSLBs,composite solid polymer electrolytes(CSPEs),derived from the incorporation of inorganic fillers into solid polymer electrolytes(SPEs),exhibit higher ionic conductivity,better mechanical strength,and superior thermal/electrochemical stability compared to the single-component SPEs,which can significantly promote the electrochemical performance of ASSLBs.Herein,the recent advances of CSPEs applied in ASSLBs are presented.The effects of the category,morphology and concentration of inorganic fillers on the ionic conductivity,mechanical strength,electrochemical window,interfacial stability and possible Li+transfer mechanism of CSPEs will be systematically discussed.Finally,the challenges and perspectives are proposed for the future development of high-performance CSPEs and ASSLBs.
基金This work was financially supported by the Key-Area Research and Development Program of Guangdong Province(Nos.2020B090919001 and 2019B090908001)the Natural Science Foundation of Guangdong Province(No.2019A1515010595)+3 种基金China Postdoctoral Science Foundation(No.2018M640778)International Cooperative Research Program of Shenzhen(No.GJHZ20180411143536149)Shenzhen Key Laboratory of Solid State Batteries(No.ZDSYS201802081843465)Guangdong Provincial Key Laboratory of Energy Materials for Electric Power(No.2018B030322001).
文摘Nano Research volume 13,pages2259–2267(2020)Cite this article 277 Accesses 1 Altmetric Metrics details Abstract The incorporation of inorganic fillers into poly(ethyleneoxide)(PEO)-based solid polymer electrolytes(SPEs)is well known as a low-cost and effective method to improve their mechanical and electrochemical properties.Porous zeolitic imidazolate framework-8(ZIF-8)is firstly used as the filler for PEO-based SPEs in this work.Due to the introduction of ZIF-8,an ionic conductivity of 2.2×10^−5 S/cm(30℃)is achieved for the composite SPE,which is one order of magnitude higher than that of the pure PEO.ZIF-8 also accounts for the broader electrochemical stability window and lithium ion transference number(0.36 at 60℃)of the composite SPE.Moreover,the improved mechanism of ZIF-8 to the composite SPE is investigated by zeta potential and Fourier transform infrared spectrograph characterizations.The stability at the composite SPE/lithium interface is greatly enhanced.The LiFePO4||Li cells using the composite SPE exhibit high capacity and excellent cycling performance at 60℃,i.e.,85%capacity retention with 111 mA·h/g capacity retained after 350 cycles at 0.5 C.In comparison,the cells using the pure PEO show fast capacity decay to 74 mA·h/g maintaining only 68 capacity.These results indicate that the PEO-based SPEs with ZIF-8 are of great promise for the application in solid-state lithium metal batteries.
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.