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
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
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
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
Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked pol...Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.展开更多
The aggregation of inorganic particles with high mass ratio will form a heterogeneous electric field in the solid polymer electrolytes(SPEs),which is difficult to be compatible with lithium anode,leading to inadequate...The aggregation of inorganic particles with high mass ratio will form a heterogeneous electric field in the solid polymer electrolytes(SPEs),which is difficult to be compatible with lithium anode,leading to inadequate ionic conductivity.Herein,a facile spray drying method is adopted to increase the mass ratio of inorganic particles and solve the aggregation problems of fillers simultaneously.The polyvinylidene fluoride(PVDF)with lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)covers the surface of each Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)granules during the nebulization process,then forming flat solid electrolytes via layer-by-layer deposition.Characterized by the atomic force microscope,the obtained solid electrolytes achieve a homogenous dispersion of Young’s modulus and surface electric field.As a result,the as-prepared SPEs present high tensile strength of 7.1 MPa,high ionic conductivity of 1.86×10^(−4)S·cm^(−1)at room temperature,and wide electrochemical window up to 5.0 V,demonstrating increased mechanical strength and uniform lithium-ion migration channels for SPEs.Thanks to the as-prepared SPEs,the lithiumsymmetrical cells show a highly stable Li plating/stripping cycling for over 1,000 h at 0.1 mA·cm^(−2).The corresponding Li/LCoO_(2)batteries also present good rate capability and excellent cyclic performance with capacity retention of 80%after 100 cycles at room temperature.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 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)by in situ polymerization are attractive due to their good interfacial contact with electrodes.Previously reported in situ polymerized SPEs,however,suffer from the low polymerization de...Solid polymer electrolytes(SPEs)by in situ polymerization are attractive due to their good interfacial contact with electrodes.Previously reported in situ polymerized SPEs,however,suffer from the low polymerization degree that causes poor mechanical strength,Li dendrite penetration,and performance decay in Li-metal batteries.Although highly polymerized SPEs are more stable than lowly polymerized ones,they are restricted by their sluggish long-chain mobility and poor ionic conductivity.In this work,a three-dimensional fibrous membrane with ion selectivity was prepared and used as a functional filler for the in situ formed SPE.The obtained SPE has high stability due to its high polymerization degree after the long-term heating process.The fibrous membrane plays a vital role in improving the SPE’s properties.The rich anion-adsorption sites on the fibrous membrane can alleviate the polarization effect and benefit a uniform current distribution at the interface.The fibrous nanostructure can efficiently interact with the polymeric matrix,providing rich hopping sites for fast Li+migration.Consequently,the obtained SPE enables a uniform Li deposition and long-term cycling performance in Li-metal batteries.This work reported an in situ formed SPE with both high polymerization degree and ionic conductivity,paving the way for designing high-performance SPEs with good comprehensive properties.展开更多
Li-ion batteries with solid polymer electrolytes(SPEs)are safer than conventional liquid electrolytes due to the absence of highly flammable liquid electrolytes.However,their performance is limited by the poor Li+tran...Li-ion batteries with solid polymer electrolytes(SPEs)are safer than conventional liquid electrolytes due to the absence of highly flammable liquid electrolytes.However,their performance is limited by the poor Li+transport in SPEs at room temperature.Anion-containing polymer-chains incorporated SPEs(ASPEs)are therefore developed to enhance Li^(+) diffusion kinetics.Herein,we propose a novel and feasible strategy to incorporate the anion-containing polymer-chains,such as lithiated perfluorinated sulfonic acid(PFSA),into polyvinylidene fluoride(PVDF)polymer-based SPEs.The immobile anion groups from the PFSA-chains impede the migration of mobile anion groups dissociated from the Li salt.The transference number is thus raised from∼0.3 to 0.52 with the introduction of anion-containing polymer-chains into SPEs.The electrostatic repulsion among anion-containing chains also reduces the close chain stacking and brings 159%increase in the ionic conductivity to 0.83×10^(−3) S/cm at 30℃ in contrast with the pure PVDF-based SPE.In addition,LiFeO_(4)/Li batteries with ASPEs exhibit 55%capacity boost at 0.5 C in contrast to the capacity of batteries with pure-PVDF SPEs,and also offer more than 1000 charge/discharge cycles.Our research findings potentially offer a facile strategy to design thermal stable SPEs with superior Li^(+) transport behaviors towards developing high-performance SPEs-based batteries.展开更多
Solid polymer electrolytes(SPEs)are one of the most promising alternatives to flammable liquid electrolytes for building safe Li metal batteries.Nevertheless,the poor ionic conductivity at room temperature(RT)and low ...Solid polymer electrolytes(SPEs)are one of the most promising alternatives to flammable liquid electrolytes for building safe Li metal batteries.Nevertheless,the poor ionic conductivity at room temperature(RT)and low resistance to Li dendrites seriously hinder the commercialization of SPEs.Herein,we design a bifunctional flame retardant SPE by combining hydroxyapatite(HAP)nanomaterials with Nmethyl pyrrolidone(NMP)in the PVDF-HFP matrix.The addition of HAP generates a hydrogen bond network with the PVDF-HFP matrix and cooperates with NMP to facilitate the dissociation of Li TFSI in the PVDF-HFP matrix.Consequently,the prepared SPE demonstrates superior ionic conductivity at RT,excellent fireproof properties,and strong resistance to Li dendrites.The assembled Li symmetric cell with prepared SPE exhibits a stable cycling performance of over 1200 h at 0.2 m A cm^(-2),and the solid-state LiFePO_4||Li cell shows excellent capacity retention of 85.3%over 600 cycles at 0.5 C.展开更多
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 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financially supported by the National Natural Science Foundation of China(Grant No.22325405,22321002,22279153)Liaoning Revitalization Talents Program(XLYC1807207,XLYC2203134)DICP I202104。
文摘Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.
基金the financial support from the National Natural Science Foundation of China(No.21805147).
文摘The aggregation of inorganic particles with high mass ratio will form a heterogeneous electric field in the solid polymer electrolytes(SPEs),which is difficult to be compatible with lithium anode,leading to inadequate ionic conductivity.Herein,a facile spray drying method is adopted to increase the mass ratio of inorganic particles and solve the aggregation problems of fillers simultaneously.The polyvinylidene fluoride(PVDF)with lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)covers the surface of each Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)granules during the nebulization process,then forming flat solid electrolytes via layer-by-layer deposition.Characterized by the atomic force microscope,the obtained solid electrolytes achieve a homogenous dispersion of Young’s modulus and surface electric field.As a result,the as-prepared SPEs present high tensile strength of 7.1 MPa,high ionic conductivity of 1.86×10^(−4)S·cm^(−1)at room temperature,and wide electrochemical window up to 5.0 V,demonstrating increased mechanical strength and uniform lithium-ion migration channels for SPEs.Thanks to the as-prepared SPEs,the lithiumsymmetrical cells show a highly stable Li plating/stripping cycling for over 1,000 h at 0.1 mA·cm^(−2).The corresponding Li/LCoO_(2)batteries also present good rate capability and excellent cyclic performance with capacity retention of 80%after 100 cycles at room temperature.
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The authors acknowledge the funding from the Shenzhen Science and Technology Program(No.RCBS20210609103647030)National Natural Science Foundation of China(Nos.22005134,12275119,and 52227802)+3 种基金Guangdong Grant(No.2021ZT09C064)Major Science and Technology Infrastructure Project of Material Genome Big-science Facilities Platform supported by the Municipal Development and Reform Commission of Shenzhen,Guangdong-Hong Kong-Macao Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices(No.2019B121205001)the Open Research Fund of Songshan Lake Materials Laboratory(No.2022SLABFK04)Guangdong Basic and Applied Basic Research Foundation(No.2021A1515012403).
文摘Solid polymer electrolytes(SPEs)by in situ polymerization are attractive due to their good interfacial contact with electrodes.Previously reported in situ polymerized SPEs,however,suffer from the low polymerization degree that causes poor mechanical strength,Li dendrite penetration,and performance decay in Li-metal batteries.Although highly polymerized SPEs are more stable than lowly polymerized ones,they are restricted by their sluggish long-chain mobility and poor ionic conductivity.In this work,a three-dimensional fibrous membrane with ion selectivity was prepared and used as a functional filler for the in situ formed SPE.The obtained SPE has high stability due to its high polymerization degree after the long-term heating process.The fibrous membrane plays a vital role in improving the SPE’s properties.The rich anion-adsorption sites on the fibrous membrane can alleviate the polarization effect and benefit a uniform current distribution at the interface.The fibrous nanostructure can efficiently interact with the polymeric matrix,providing rich hopping sites for fast Li+migration.Consequently,the obtained SPE enables a uniform Li deposition and long-term cycling performance in Li-metal batteries.This work reported an in situ formed SPE with both high polymerization degree and ionic conductivity,paving the way for designing high-performance SPEs with good comprehensive properties.
基金supported by the National Natural Science Foundation of China(Nos.51972043 and 52102212)the Sichuan-Hong Kong Collaborative Research Fund(No.2021YFH0184)+1 种基金the Foundation of Yangtze Delta Region Institute(Huzhou)of UESTC,China(Nos.U03210010 and U03210028)Huzhou Science and Technology Special Representative Project(No.2021KT54).
文摘Li-ion batteries with solid polymer electrolytes(SPEs)are safer than conventional liquid electrolytes due to the absence of highly flammable liquid electrolytes.However,their performance is limited by the poor Li+transport in SPEs at room temperature.Anion-containing polymer-chains incorporated SPEs(ASPEs)are therefore developed to enhance Li^(+) diffusion kinetics.Herein,we propose a novel and feasible strategy to incorporate the anion-containing polymer-chains,such as lithiated perfluorinated sulfonic acid(PFSA),into polyvinylidene fluoride(PVDF)polymer-based SPEs.The immobile anion groups from the PFSA-chains impede the migration of mobile anion groups dissociated from the Li salt.The transference number is thus raised from∼0.3 to 0.52 with the introduction of anion-containing polymer-chains into SPEs.The electrostatic repulsion among anion-containing chains also reduces the close chain stacking and brings 159%increase in the ionic conductivity to 0.83×10^(−3) S/cm at 30℃ in contrast with the pure PVDF-based SPE.In addition,LiFeO_(4)/Li batteries with ASPEs exhibit 55%capacity boost at 0.5 C in contrast to the capacity of batteries with pure-PVDF SPEs,and also offer more than 1000 charge/discharge cycles.Our research findings potentially offer a facile strategy to design thermal stable SPEs with superior Li^(+) transport behaviors towards developing high-performance SPEs-based batteries.
基金supported by the National Natural Science Foundation of China (Grant Nos.51604089,51874110,22173066,21903058)the Natural Science Foundation of Heilongjiang Province (Grant No.YQ2021B004)Open Project of State Key Laboratory of Urban Water Resource and Environment (Grant No.QA202138)。
文摘Solid polymer electrolytes(SPEs)are one of the most promising alternatives to flammable liquid electrolytes for building safe Li metal batteries.Nevertheless,the poor ionic conductivity at room temperature(RT)and low resistance to Li dendrites seriously hinder the commercialization of SPEs.Herein,we design a bifunctional flame retardant SPE by combining hydroxyapatite(HAP)nanomaterials with Nmethyl pyrrolidone(NMP)in the PVDF-HFP matrix.The addition of HAP generates a hydrogen bond network with the PVDF-HFP matrix and cooperates with NMP to facilitate the dissociation of Li TFSI in the PVDF-HFP matrix.Consequently,the prepared SPE demonstrates superior ionic conductivity at RT,excellent fireproof properties,and strong resistance to Li dendrites.The assembled Li symmetric cell with prepared SPE exhibits a stable cycling performance of over 1200 h at 0.2 m A cm^(-2),and the solid-state LiFePO_4||Li cell shows excellent capacity retention of 85.3%over 600 cycles at 0.5 C.