首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 93 毫秒
1.
Single salt polymer electrolytes based on hexanoyl chitosan‐ENR25 were prepared by employing LiN (CF3SO2)2 or LiCF3SO3 as the doping salt. Elastic property of hexanoyl chitosan was enhanced with the incorporation of ENR25. DSC studies revealed immiscibility of hexanoyl chitosan and ENR25, and dissolution of salt was favored in ENR25 phase. Conductivity enhancement was observed in the blends as compared with the neat hexanoyl chitosan. The maximum conductivities achieved for LiCF3SO3‐ and LiN (CF3SO2)2‐comprising electrolyte systems were 1.6 × 10?8 and 5.0 × 10?7 S cm?1, respectively. Deconvolution of spectra bands in the vas (SO2?) mode of LiN (CF3SO2)2 and vs (SO3?) mode of LiCF3SO3 has been carried out to estimate the relative percentage of free ions and associated ions. The findings were in good agreement with conductivity results. Electrical double layer capacitor (EDLC) was fabricated with hexanoyl chitosan/ENR25 (90:10)‐LiN (CF3SO2)2‐EmImTFSI electrolyte and activated carbon‐based electrodes. The conductivity and electrochemical stability window of hexanoyl chitosan/ENR25‐LiN (CF3SO2)2‐EmImTFSI were ~10?6 S cm?1 and 2.7 V, respectively. The performance of the EDLC was analyzed by cyclic voltammetry (CV) and galvanostatic charge‐discharge (GCD). From GCD, the specific capacitance of EDLC was 58.0 F g?1 at 0.6 mA cm?2. The specific capacitance was found to decrease with increasing current density.  相似文献   

2.
In the present work, nanofibrous composite polymer electrolytes consist of polyethylene oxide (PEO), ethylene carbonate (EC), propylene carbonate (PC), lithium perchlorate (LiClO4), and titanium dioxide (TiO2) were designed using response surface method (RSM) and synthesized via an electrospinning process. Morphological properties of the as‐prepared electrolytes were studied using SEM. FTIR spectroscopy was conducted to investigate the interaction between the components of the composites. The highest room temperature ionic conductivity of 0.085 mS.cm?1 was obtained with incorporation of 0.175 wt. % TiO2 filler into the plasticized nanofibrous electrolyte by EC. Moreover, the optimum structure was compared with a film polymeric electrolyte prepared using a film casting method. Despite more amorphous structure of the film electrolyte, the nanofibrous electrolyte showed superior ion conductivity possibly due to the highly porous structure of the nanofibrous membranes. Furthermore, the mechanical properties illustrated slight deterioration with incorporation of the TiO2 nanoparticles into the electrospun electrolytes. This investigation indicated the great potential of the electrospun structures as all‐solid‐state polymeric electrolytes applicable in lithium ion batteries.  相似文献   

3.
Silver polymer electrolytes were prepared by blending silver salt with poly(oxyethylene)9 methacrylate)‐graft‐poly(dimethyl siloxane), POEM‐g‐PDMS, confining silver salts within the continuous ion‐conducting POEM domains of microphase‐separated graft copolymer. AgClO4 polymer electrolytes exhibited their maximum conductivity at high silver concentrations as well as higher ionic conductivities than AgCF3SO3 electrolytes. The difference in conductivities of the two electrolytes was investigated in terms of the differences in the interactions of silver ions with ether oxygen of POEM and, hence, with the anions of salts. Upon the addition of salt in graft copolymer, the increase of Tg in AgClO4 was higher than that in AgCF3SO3 electrolytes. Analysis of an extended configuration entropy model revealed that the interaction of ether oxygen/AgClO4 was stronger than that of ether oxygen/AgCF3SO3 whereas the interaction of Ag+/ClO4? was weaker than that of Ag+/CF3SO3?. These interactions are supported by the anion vibration mode of FT‐Raman spectroscopy. It is thus concluded that the higher ionic conductivity of AgClO4 electrolytes was mostly because of higher concentrations of free ions, resulting from their strong ether oxygen/silver ion and weak silver ion/anion interactions. A small angle X‐ray scattering study also showed that the connectivity of the POEM phase was well developed to form nanophase morphology and the domain periodicities of graft copolymer electrolytes monotonically increased with the increase of silver concentration up to critical concentrations, after which the connectivity was less developed and the domain spacings remained invariant. This is attributed to the fact that silver salts are spatially and selectively incorporated in conducting POEM domains as free ions up to critical concentrations, after which they are distributed in both domains as ion pairs without selectivity. The increase of domain d‐spacing in AgClO4 electrolytes was larger than that in AgCF3SO3, which again results from high concentrations of free ions in the former. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1018–1025, 2007  相似文献   

4.
Composite polymer electrolyte (CPE) films consisting of PEO, LiClO4, and Li1.3Al0.3Ti1.7(PO4)3 with fixed EO/Li = 8 but different relative compositions of the two lithium salts were prepared by the solution casting method. The CPE films were characterized using SEM, DSC, electrical impedance spectroscopy (EIS), and ion transference number measurement. It was found that the incorporation of LiClO4 and Li1.3Al0.3Ti1.7(PO4)3 into PEO by keeping EO/Li = 8 reduced the crystallinity of PEO from 50.34% to the range of 3.57–15.63% depending upon the relative composition of the two salts. The room temperature impedance spectra of the CPE films all exhibited a shape of depressed semicircle in the high frequency range and inclined line in the low frequency range, but the high temperature ones were mainly inclined lines. The Li+ ionic conductivity of the CPE films mildly increased and then decreased with increasing Li1.3Al0.3Ti1.7(PO4)3 content, and the maximum conductivities were obtained at Li1.3Al0.3Ti1.7(PO4)3 content of 15 wt % for all measuring temperatures, for example, 1.378 × 10?3 S/cm at 100 °C and 1.387 × 10?5 S/cm at 25 °C. The temperature dependence of the ionic conductivity of the CPE films follows the Vogel–Tamman–Fulcher (VTF) equation The pseudo activation energies (Ea) were rather low, 0.053–0.062 eV, indicating an easy migration of Li+ in the amorphous phase dominant PEO. The pre‐exponent constant A and ion transference number tLi+ were found to have a similar variation tendency with increasing Li1.3Al0.3Ti1.7(PO4)3 content and reached their maximums also at Li1.3Al0.3Ti1.7(PO4)3 content of 15 wt %. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 743–751, 2005  相似文献   

5.
The properties of polymeric materials are dictated not only by their composition but also by their molecular architecture. Here, by employing brush‐first ring‐opening metathesis polymerization (ROMP), norbornene‐terminated poly(ethylene oxide) (PEO) macromonomers ( MM‐n , linear architecture), bottlebrush polymers ( Brush‐n , comb architecture), and brush‐arm star polymers ( BASP‐n , star architecture), where n indicates the average degree of polymerization (DP) of PEO, are synthesized. The impact of architecture on the thermal properties and Li+ conductivities for this series of PEO architectures is investigated. Notably, in polymers bearing PEO with the highest degree of polymerization, irrespective of differences in architecture and molecular weight (~100‐fold differences), electrolytes with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as an Li+ source exhibit normalized ionic conductivities (σn) within only 4.9 times difference (σn = 29.8 × 10?5 S cm?1 for MM‐45 and σn = 6.07 × 10?5 S cm?1 for BASP‐45 ) at a concentration of Li+ r = [Li+]/[EO] = 1/12 at 50 °C. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 448–455  相似文献   

6.
Ceramic fast-ion conductors have high ionic conductivities (>10?4 S cm?1) but are difficult to process and have poor chemo/mechanical properties at the electrode/electrolyte interfaces. In contrast, polymer electrolytes are pliable and easy to process but suffer from low room-temperature ionic conductivities (≈10?6-10?7 S cm?1). Combining these two elements to form a composite polymer electrolyte is a promising way to enable all-solid-state lithium-metal batteries. The choice of ceramic filler and polymer can be tailored to provide synergistic benefits that overcome the practical shortcomings of the two components. Herein, the fundamentals of Li+ conduction through the various phases and interfaces in these materials are discussed as well as the important parameters, beyond the initial choice of polymer and ceramic filler materials that must be considered while designing composite polymer electrolytes. Emphasis is placed on the particle filler engineering and practical fabrication methods as routes toward enhancing the properties of these composites.  相似文献   

7.
Li+‐conducting oxides are considered better ceramic fillers than Li+‐insulating oxides for improving Li+ conductivity in composite polymer electrolytes owing to their ability to conduct Li+ through the ceramic oxide as well as across the oxide/polymer interface. Here we use two Li+‐insulating oxides (fluorite Gd0.1Ce0.9O1.95 and perovskite La0.8Sr0.2Ga0.8Mg0.2O2.55) with a high concentration of oxygen vacancies to demonstrate two oxide/poly(ethylene oxide) (PEO)‐based polymer composite electrolytes, each with a Li+ conductivity above 10?4 S cm?1 at 30 °C. Li solid‐state NMR results show an increase in Li+ ions (>10 %) occupying the more mobile A2 environment in the composite electrolytes. This increase in A2‐site occupancy originates from the strong interaction between the O2? of Li‐salt anion and the surface oxygen vacancies of each oxide and contributes to the more facile Li+ transport. All‐solid‐state Li‐metal cells with these composite electrolytes demonstrate a small interfacial resistance with good cycling performance at 35 °C.  相似文献   

8.
Organic-inorganic hybrid membranes based on poly(ethylene oxide) (PEO) 6.25 wt%/poly(vinylidene fluoride hexa fluoro propylene) [P(VdF-HFP)] 18.75 wt% were prepared by using various concentration of nanosized barium titanate (BaTiO3) filler. Structural characterizations were made by X-ray diffraction and Fourier transform infrared spectroscopy, which indicate the inclusion of BaTiO3 in to the polymer matrix. Addition of filler creates an effective route of polymer-filler interface and promotes the ionic conductivity of the membranes. From the ionic conductivity results, 6 wt% of BaTiO3-incorporated composite polymer electrolyte (CPE) showed the highest ionic conductivity (6 × 10?3 Scm?1 at room temperature). It is found that the filler content above 6 wt% rendered the membranes less conducting. Morphological images reveal that the ceramic filler was embedded over the membrane. Thermogravimetric and differential thermal analysis (TG-DTA) of the CPE sample with 6 wt% of the BaTiO3 shows high thermal stability. Electrochemical performance of the composite polymer electrolyte was studied in LiFePO4/CPE/Li coin cell. Charge-discharge cycle has been performed for the film exhibiting higher conductivity. These properties of the nanocomposite electrolyte are suitable for Li-batteries.  相似文献   

9.
The present work is focused on gelatin‐based electrolytes doped with a range of concentration of zinc triflate (Zn(CF3SO3)2). The transparent‐thin‐film samples have been represented by the notation GelatinnZn(CF3SO3)2, where n represents the zinc triflate salt concentration in the electrolyte membranes from 0.00 wt% to 10.93 wt% . The samples have been characterized by conductivity measurements, thermal analysis, cyclic voltammetry, X‐ray diffraction (XRD), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The gelatin‐based electrolytes were also tested as ionic conductors in electrochromic devices with the glass/ITO/WO3/gelatin‐based electrolyte/CeO2‐TiO2/ITO/glass configuration.  相似文献   

10.
程琥  朱昌宝  杨勇 《化学学报》2007,65(24):2832-2838
通过FTIR光谱技术对P(EO)nLiX [X=N(SO2CF3)2, SCN, ClO4] (n=4~60)聚合物电解质的离子缔合行为进行了研究, 结果表明在PEO-LiSCN体系中缔合现象较为严重. 在高浓度时LiSCN主要以离子对、离子簇以及二聚体形式存在, 自由离子含量较少. 而对于LiTFSI和LiClO4体系, 则以自由离子形式为主. 随着锂盐的加入, 由于其阴离子的增塑作用使聚氧化乙烯(PEO)中的晶相成分逐渐向无定形相转化. 当锂盐含量增加到一定程度, 体系中会有不同晶相复合物的形成.  相似文献   

11.
Electrolytes with high lithium-ion conductivity, better mechanical strength and large electrochemical window are essential for the realization of high-energy density lithium batteries. Polymer electrolytes are gaining interest due to their inherent flexibility and nonflammability over conventional liquid electrolytes. In this work, lithium garnet composite polymer electrolyte membrane (GCPEM) consisting of large molecular weight (Wavg ~?5?×?106) polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO4) and lithium garnet oxide Li6.28Al0.24La3Zr2O12 (Al-LLZO) is prepared by solution-casting method. Significant improvement in Li+ conductivity for Al-LLZO containing GCPEM is observed compared with the Al-LLZO free polymer membrane. Maximized room temperature (30 °C) Li+ conductivity of 4.40?×?10?4 S cm?1 and wide electrochemical window (4.5 V) is observed for PEO8/LiClO4?+?20 wt% Al-LLZO (GCPEM-20) membrane. The fabricated cell with LiCoO2 as cathode, metallic lithium as anode and GCPEM-20 as electrolyte membrane delivers an initial charge/discharge capacity of 146 mAh g?1/142 mAh g?1 at 25 °C with 0.06 C-rate.  相似文献   

12.
Polymer electrolytes composed of a blend of polyvinyl chloride-polyethylene oxide (PVC-PEO) as a host polymer, lithium triflate (LiCF3SO3) as a salt, mixture of ethylene carbonate (EC) and dibuthyl phthalate (DBP) as plasticizers and silica (SiO2) as the nanocomposite filler were studied. Results suggest that PVC-PEO blending exhibits improved mechanical strength compared to that of pure PEO. The introduction of LiCF3SO3 changes the mechanical properties of PVC-PEO blends from hard and brittle to soft and tough. In PVC-PEO:LiCF3SO3 (70:30) system, the Young’s modulus value decreases from 5.30 × 10−1 MPa to 4.78 × 10−4 MPa and the elongation at peak value increases from 3.71 mm to 32.09 mm with the incorporation of DBP and EC. The deteriorated mechanical properties with the addition of plasticizers are overcome with the addition of SiO2 as nanocomposite filler. In PVC-PEO-LiCF3SO3-DBP-EC system, the addition of 5% SiO2 increases the Young’s modulus value from 4.78 × 10−4 MPa to 1.51 × 10−3 MPa. The improvement of the mechanical properties reveals greater dispersion of SiO2 particles in PVC-PEO blend based polymer electrolytes. In practical lithium polymer cells, inorganic fillers are frequently added to improve the mechanical strength of the electrolyte films.  相似文献   

13.
A novel single lithium‐ion (Li‐ion) conducting polymer electrolyte is presented that is composed of the lithium salt of a polyanion, poly[(4‐styrenesulfonyl)(trifluoromethyl(S‐trifluoromethylsulfonylimino)sulfonyl)imide] (PSsTFSI?), and high‐molecular‐weight poly(ethylene oxide) (PEO). The neat LiPSsTFSI ionomer displays a low glass‐transition temperature (44.3 °C; that is, strongly plasticizing effect). The complex of LiPSsTFSI/PEO exhibits a high Li‐ion transference number (tLi+=0.91) and is thermally stable up to 300 °C. Meanwhile, it exhibits a Li‐ion conductivity as high as 1.35×10?4 S cm?1 at 90 °C, which is comparable to that for the classic ambipolar LiTFSI/PEO SPEs at the same temperature. These outstanding properties of the LiPSsTFSI/PEO blended polymer electrolyte would make it promising as solid polymer electrolytes for Li batteries.  相似文献   

14.
All-solid-state polymer lithium-ion batteries are ideal choice for the next generation of rechargeable lithium-ion batteries due to their high energy, safety and flexibility. Among all polymer electrolytes, PEO-based polymer electrolytes have attracted extensive attention because they can dissolve various lithium salts. However, the ionic conductivity of pure PEO-based polymer electrolytes is limited due to high crystallinity and poor segment motion. An inorganic filler SiO2 nanospheres and a plasticizer Succinonitrile (SN) are introduced into the PEO matrix to improve the crystallization of PEO, promote the formation of amorphous region, and thus improve the movement of PEO chain segment. Herein, a PEO18−LiTFSI−5 %SiO2−5 %SN composite solid polymer electrolyte (CSPE) was prepared by solution-casting. The high ionic conductivity of the electrolyte was demonstrated at 60 °C up to 3.3×10−4 S cm−1. Meanwhile, the electrochemical performance of LiFePO4/CSPE/Li all-solid-state battery was tested, with discharge capacity of 157.5 mAh g−1 at 0.5 C, and capacity retention rate of 99 % after 100 cycles at 60 °C. This system provides a feasible strategy for the development of efficient all-solid-state lithium-ion batteries.  相似文献   

15.
A new plasticized nanocomposite polymer electrolyte based on poly (ethylene oxide) (PEO)-LiTf dispersed with ceramic filler (Al2O3) and plasticized with propylene carbonate (PC), ethylene carbonate (EC), and a mixture of EC and PC (EC+PC) have been studied for their ionic conductivity and thermal properties. The incorporation of plasticizers alone will yield polymer electrolytes with enhanced conductivity but with poor mechanical properties. However, mechanical properties can be improved by incorporating ceramic fillers to the plasticized system. Nanocomposite solid polymer electrolyte films (200–600 μm) were prepared by common solvent-casting method. In present work, we have shown the ionic conductivity can be substantially enhanced by using the combined effect of the plasticizers as well as the inert filler. It was revealed that the incorporating 15 wt.% Al2O3 filler in to PEO: LiTf polymer electrolyte significantly enhanced the ionic conductivity [σ RT (max)?=?7.8?×?10?6 S cm?1]. It was interesting to observe that the addition of PC, EC, and mixture of EC and PC to the PEO: LiTf: 15 wt.% Al2O3 CPE showed further conductivity enhancement. The conductivity enhancement with EC is higher than PC. However, mixture of plasticizer (EC+PC) showed maximum conductivity enhancement in the temperature range interest, giving the value [σ RT (max)?=?1.2?×?10?4 S cm?1]. It is suggested that the addition of PC, EC, or a mixture of EC and PC leads to a lowering of glass transition temperature and increasing the amorphous phase of PEO and the fraction of PEO-Li+ complex, corresponding to conductivity enhancement. Al2O3 filler would contribute to conductivity enhancement by transient hydrogen bonding of migrating ionic species with O–OH groups at the filler grain surface. The differential scanning calorimetry thermograms points towards the decrease of T g , crystallite melting temperature, and melting enthalpy of PEO: LiTf: Al2O3 CPE after introducing plasticizers. The reduction of crystallinity and the increase in the amorphous phase content of the electrolyte, caused by the filler, also contributes to the observed conductivity enhancement.  相似文献   

16.
In the system LiSO3CF3/RbSO3CF3 four different quasi‐ternary phases occur: Li0.7Rb0.3SO3CF3, Li0.55Rb0.45SO3CF3, LiRb2(SO3CF3)3, and Li0.2Rb0.8SO3CF3. These have been identified, and characterized by means of X‐ray powder diffractometry and DSC. LiSO3CF3 is trimorphic, LiRb2(SO3CF3)3 is dimorphic and RbSO3CF3 exists in four different modifications. The cation dynamics has been studied using 7Li‐NMR line shape analysis and 7Li‐spin lattice relaxation (T1) measurements. The pure and mixed trifluoromethylsulfonates in the system LiSO3CF3/RbSO3CF3 are solid electrolytes. Their ionic conductivities below 475 K increase with the rubidium content. Above this temperature, the conductivity of β‐LiRb2(SO3CF3)3 exceeds the one of δ‐RbSO3CF3.  相似文献   

17.
The composite polymer electrolyte (CPE) membranes, comprising of poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP), aluminum oxyhydroxide, (AlO[OH]n) of two different particle sizes 7 μm/14 nm and LiN(CF3SO2)2 as lithium salt were prepared using solution casting technique. The prepared membranes were subjected to XRD, impedance spectroscopy, compatibility and transport number studies. The incorporation of nanofiller greatly enhanced the ionic conductivity and the compatibility of the composite polymer electrolyte. Also LiCr0.01Mn1.99O4/CPE/Li cells were assembled and their charge-discharge profiles have been made at 70 °C. The film which possesses nanosized filler offered better electrochemical properties than those with micron sized filler. The results are discussed based on Lewis acid-base theory.  相似文献   

18.
Details on the structure and transport characteristics of the solid polymer electrolyte polyethylene oxide (PEO)/lithium salt (LiClO4) modified by novolac phenolic resin are presented here. From IR spectra it could be concluded that complex formation occurred through multiple interactions between the ether oxygen of PEO–lithium, phenolic lithium, and the phenolic ether oxygen of PEO. The free hydroxyl band in phenolic reflected that phenolic closely interacted with both the PEO polymer and ionic salt. With increasing salt content in PEO, the vibration band corresponding to the ClO anion (~623 cm?1) displayed growth of a shoulder at ~635 cm?1, suggesting the formation of Li+…ClO4? ion pairing. However, in the presence of phenolic, ion‐pairing formation was effectively suppressed, which suggested that the phenolic moiety facilitated a greater degree of LiClO4 salt dissociation. Activation energy analysis revealed two conducting pathways: one through the amorphous PEO and the other through the PEO/phenolic amorphous matrix. The high ion conductivity originated from effective salt dissociation and the establishment of a new conduction network formed by PEO and phenolic. Furthermore, the structural modification also extended the thermal stability and mechanical strength of the solid polymer electrolyte composite. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3866–3875, 2004  相似文献   

19.
The newly created porous inorganic particles Li4.7Ag1.63GeS4.8 as filler are added into poly (ethylene oxide) (PEO) with LiTFSI salt, which greatly improves the electrochemical stability of solid-state PEO-based electrolytes against Li metal in a working battery. Due to many pores and channels in the filler, Li dendrites would grow along these channels thereby effectively inhibiting their fast spread in PEO matrix and retarding the short circuit on account of the penetration of Li dendrite. The Li+ conductivity of this solid-state electrolyte membrane could be 1.36 × 10-4 S/cm at 40 °C. The fabricated symmetrical Li metal cells could cycle above 550 h at 0.05 mA/cm2 and corresponding LiFePO4/Li all-solid-state cells have an excellent cycling stability of 160.65 mAh g-1 specific capacity after 200 cycles with 99.93% columbic efficiency at 50 °C environment.  相似文献   

20.
This paper focus on the effect of nanosize (<50 nm BET) inorganic alumina (Al2O3) filler on the structural, conductivity, and thermal properties of chitosan‐based polymer electrolytes. Films of chitosan and its complexes were prepared using solution‐casting technique. Different amounts of Al2O3 viz., 3, 4.5, 6, 7.5, 9, 12, and 15 wt% were added to the highest room temperature conducting sample in the chitosan–salt system, i.e. sample containing 60 wt% chitosan–40 wt% NH4SCN. The conductivity value of the sample is 1.29 × 10?4 S cm?1. On addition of 6 wt% Al2O3 filler the ionic conductivity increased to 5.86 × 10?4 S cm?1. The amide and amino peaks in the spectrum of chitosan at 1636 and 1551 cm?1, respectively, shift to lower wavenumbers on addition of salt. The glass transition temperature Tg for the highest conducting composite is 190°C. The increase in Tg with increase in more than 6 wt% filler content is attributed to the increase in degree of crystallinity as proven from X‐ray diffraction studies. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号