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
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
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
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
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
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
Solid polymer electrolytes(SPEs)possess comprehensive advantages such as high flexibility,low interfacial resistance with the electrodes,excellent film-forming ability,and low price,however,their applications in solid...Solid polymer electrolytes(SPEs)possess comprehensive advantages such as high flexibility,low interfacial resistance with the electrodes,excellent film-forming ability,and low price,however,their applications in solid-state batteries are mainly hindered by the insufficient ionic conductivity especially below the melting temperatures,etc.To improve the ion conduction capability and other properties,a variety of modification strategies have been exploited.In this review article,we scrutinize the structure characteristics and the ion transfer behaviors of the SPEs(and their composites)and then disclose the ion conduction mechanisms.The ion transport involves the ion hopping and the polymer segmental motion,and the improvement in the ionic conductivity is mainly attributed to the increase of the concentration and mobility of the charge carriers and the construction of fast-ion pathways.Furthermore,the recent advances on the modification strategies of the SPEs to enhance the ion conduction from copolymer structure design to lithium salt exploitation,additive engineering,and electrolyte micromorphology adjustion are summarized.This article intends to give a comprehensive,systemic,and profound understanding of the ion conduction and enhancement mechanisms of the SPEs for their viable applications in solid-state batteries with high safety and energy density.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
Solid polymer electrolytes(SPEs)possess several merits including no leakage,ease in process,and suppressing lithium dendrites growth.These features are beneficial for improving the cycle life and safety performance of...Solid polymer electrolytes(SPEs)possess several merits including no leakage,ease in process,and suppressing lithium dendrites growth.These features are beneficial for improving the cycle life and safety performance of rechargeable lithium metal batteries(LMBs),as compared to conventional non-aqueous liquid electrolytes.Particularly,the superior elasticity of polymeric material enables the employment of SPEs in building ultra-thin and flexible batteries,which could further expand the application scenarios of high-energy rechargeable LMBs.In this perspective,recent progresses on ion transport mechanism of SPEs and structural designs of electrolyte components(e.g.conductive lithium salts,polymer matrices)are scrutinized.In addition,key achievements in the field of single lithium-ion conductive SPEs are also outlined,aiming to provide the status quo in those SPEs with high selectivity in cationic transport.Finally,possible strategies for improving the performance of SPEs and their rechargeable LMBs are also discussed.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
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
Synthesis and ion transport properties of hot-pressed solid polymer electrolytes (SPEs), (l-x) PEO: x KI, where x is the content of KI in wt%, are reported. A hot-press technique has been used for the formation o...Synthesis and ion transport properties of hot-pressed solid polymer electrolytes (SPEs), (l-x) PEO: x KI, where x is the content of KI in wt%, are reported. A hot-press technique has been used for the formation of the polymeric membranes in place of the usual solution cast method. The composition (80 PEO:20 KI) was identified as the highest conducting polymer electrolyte on the basis of compositional dependent conductivity studies of PEO:KI films. A conductivity enhancement of more than two orders of magnitude from that of the pure PEO was achieved. Materials characterization and ion transport mechanism were explained by using various experimental techniques.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
For All-Solid-State battery applications, Mg2+-ion conducting polymer electrolytes and Mg-metal electrode are currently considered as alternate choices in place of Li+-ion conducting polymer electrolytes/Li-metal el...For All-Solid-State battery applications, Mg2+-ion conducting polymer electrolytes and Mg-metal electrode are currently considered as alternate choices in place of Li+-ion conducting polymer electrolytes/Li-metal electrode. Present paper reports fabrication of All-Solid-State battery based on the following Mg2+-ion conducting nano composite polymer electrolyte (NCPE) films: [85PEO: 15Mg(C104)2] + 5% TiO2 (〈 100 nm), [85PEO: 15Mg(CIO4)2] + 3% SiO2(-8 nm). [85PEO: 15Mg(CIO4)2] + 3% MgO (〈 100 nm), [85PEO:15Mg(C1O4)2] + 3% MgO (-44 μm). NCPE films were prepared by hot-press technique. Solid Polymer Electrolyte (SPE) composition: [85PEO: 15Mg(CIO4)2], identified as high conducting film at room temperature, has been used as ISt--phase host and nano/micro particles of active (MgO)/passive (SiO2, TiO2) fillers as IInd-phase dispersoid. Filler particle dependent conductivity studies identified above mentioned NCPE films as optimum conducting composition (OCC) at room temperature. Ion transport behavior of SPE/NCPE film materials was investigated previously. Present paper reports materials characterization and cell performance studies on All-Solid-State batteries: Mg (Anode) Ⅱ SPE or NCPE films tt C+MnO2+Electrolyte (Cathode). Open circuit voltage (OCV) obtained was in the range: 1.79-1.92 V. The batteries were discharged at room temperature under different load conditions and some important battery parameters have been evaluated from plateau region of cell-potential discharge profiles. All the batteries performed quite satisfactorily specially under low current drain states.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This work was supported partially by project of the State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources(Nos.LAPS21004 and LAPS202114)the Hebei Natural Science Foundation(No.E2022502022)+5 种基金the National Natural Science Foundation of China(Nos.52272200,51972110,52102245,and 52072121)the Beijing Science and Technology Project(No.Z211100004621010)the Beijing Natural Science Foundation(Nos.2222076 and 2222077)the Huaneng Group Headquarters Science and Technology Project(No.HNKJ20-H88)the 2022 Strategic Research Key Project of Science and Technology Commission of the Ministry of Education,the China Postdoctoral Science Foundation(No.2022M721129)the Fundamental Research Funds for the Central Universities(Nos.2022MS030,2021MS028,2020MS023,and 2020MS028),and the NCEPU“Double First-Class”Program.
文摘Solid polymer electrolytes(SPEs)possess comprehensive advantages such as high flexibility,low interfacial resistance with the electrodes,excellent film-forming ability,and low price,however,their applications in solid-state batteries are mainly hindered by the insufficient ionic conductivity especially below the melting temperatures,etc.To improve the ion conduction capability and other properties,a variety of modification strategies have been exploited.In this review article,we scrutinize the structure characteristics and the ion transfer behaviors of the SPEs(and their composites)and then disclose the ion conduction mechanisms.The ion transport involves the ion hopping and the polymer segmental motion,and the improvement in the ionic conductivity is mainly attributed to the increase of the concentration and mobility of the charge carriers and the construction of fast-ion pathways.Furthermore,the recent advances on the modification strategies of the SPEs to enhance the ion conduction from copolymer structure design to lithium salt exploitation,additive engineering,and electrolyte micromorphology adjustion are summarized.This article intends to give a comprehensive,systemic,and profound understanding of the ion conduction and enhancement mechanisms of the SPEs for their viable applications in solid-state batteries with high safety and energy density.
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The authors gratefully acknowledge the financial support provided by the Fundamental Research Funds for Central Universities,HUST(2020kfyXJJS095).
文摘Solid polymer electrolytes(SPEs)possess several merits including no leakage,ease in process,and suppressing lithium dendrites growth.These features are beneficial for improving the cycle life and safety performance of rechargeable lithium metal batteries(LMBs),as compared to conventional non-aqueous liquid electrolytes.Particularly,the superior elasticity of polymeric material enables the employment of SPEs in building ultra-thin and flexible batteries,which could further expand the application scenarios of high-energy rechargeable LMBs.In this perspective,recent progresses on ion transport mechanism of SPEs and structural designs of electrolyte components(e.g.conductive lithium salts,polymer matrices)are scrutinized.In addition,key achievements in the field of single lithium-ion conductive SPEs are also outlined,aiming to provide the status quo in those SPEs with high selectivity in cationic transport.Finally,possible strategies for improving the performance of SPEs and their rechargeable LMBs are also discussed.
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financially supported by DST, New Delhi through the ‘Fast Track Young Scientist Research Project’(No. SR/FTP/PS-23/2009)
文摘Synthesis and ion transport properties of hot-pressed solid polymer electrolytes (SPEs), (l-x) PEO: x KI, where x is the content of KI in wt%, are reported. A hot-press technique has been used for the formation of the polymeric membranes in place of the usual solution cast method. The composition (80 PEO:20 KI) was identified as the highest conducting polymer electrolyte on the basis of compositional dependent conductivity studies of PEO:KI films. A conductivity enhancement of more than two orders of magnitude from that of the pure PEO was achieved. Materials characterization and ion transport mechanism were explained by using various experimental techniques.
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.
文摘For All-Solid-State battery applications, Mg2+-ion conducting polymer electrolytes and Mg-metal electrode are currently considered as alternate choices in place of Li+-ion conducting polymer electrolytes/Li-metal electrode. Present paper reports fabrication of All-Solid-State battery based on the following Mg2+-ion conducting nano composite polymer electrolyte (NCPE) films: [85PEO: 15Mg(C104)2] + 5% TiO2 (〈 100 nm), [85PEO: 15Mg(CIO4)2] + 3% SiO2(-8 nm). [85PEO: 15Mg(CIO4)2] + 3% MgO (〈 100 nm), [85PEO:15Mg(C1O4)2] + 3% MgO (-44 μm). NCPE films were prepared by hot-press technique. Solid Polymer Electrolyte (SPE) composition: [85PEO: 15Mg(CIO4)2], identified as high conducting film at room temperature, has been used as ISt--phase host and nano/micro particles of active (MgO)/passive (SiO2, TiO2) fillers as IInd-phase dispersoid. Filler particle dependent conductivity studies identified above mentioned NCPE films as optimum conducting composition (OCC) at room temperature. Ion transport behavior of SPE/NCPE film materials was investigated previously. Present paper reports materials characterization and cell performance studies on All-Solid-State batteries: Mg (Anode) Ⅱ SPE or NCPE films tt C+MnO2+Electrolyte (Cathode). Open circuit voltage (OCV) obtained was in the range: 1.79-1.92 V. The batteries were discharged at room temperature under different load conditions and some important battery parameters have been evaluated from plateau region of cell-potential discharge profiles. All the batteries performed quite satisfactorily specially under low current drain states.