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1.
To realize polymer electrolytes with high ionic conductivity, we exploited the high ionic conductivity of an ionic liquid. In situ free radical polymerization of compatible vinyl monomers in a room temperature ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfonyl)imide (EMITFSI), afforded a novel series of polymer electrolytes. Polymer gels obtained by the polymerization of methyl methacrylate (MMA) in EMITFSI in the presence of a small amount of a cross-linker gave self-standing, flexible, and transparent films. The glass transition temperatures of the gels, which we named "ion gels", decreased with increasing mole fraction of EMITFSI and behaved as a completely compatible binary system of poly(methyl methacrylate) (PMMA) and EMITFSI. The temperature dependence of the ionic conductivity of the ion gels followed the Vogel-Tamman-Fulcher (VTF) equation, and the ionic conductivity at ambient temperature reached a value close to 10(-2) S cm(-1). Similarly to the behavior of the ionic liquid, the cation in the ion gels diffused faster than the anion. The number of carrier ions, calculated from the Nernst-Einstein equation, was found to increase for an ion gel from the corresponding value for the ionic liquid itself. The cation transference number increased with decreasing EMITFSI concentration due to interaction between the PMMA matrix and the TFSI(-) anion, which prohibited the formation of ion clusters or associates, as was the case for the ionic liquid itself.  相似文献   

2.
To study the ion‐conductive and dielectric properties of polymer electrolytes based on poly(ethylene carbonate) (PEC) with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), the complex permittivity and conductivity were measured using broadband dielectric spectroscopy. The temperature dependence of the relaxation frequency and ionic conductivity for PEC‐LiTFSI electrolytes (1 – 200 mol%) indicates that the segmental motion of PEC chains decreases with the addition of just 1 mol% of Li salt and increases with increasing concentration above 10 mol%. According to the Walden rule for PEC‐based electrolytes, the value of deviation from the reference line increased, and the fragility and decoupling exponents decreased with increasing salt concentration. These results indicate that there are large numbers of ion pairs and aggregated ions, which imply low ionicity and reduced fragility in highly concentrated PEC‐based electrolytes. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

3.
The Li+ environment and transport in an ionic liquid (IL) comprised of Li+ and an anion of bis(trifluoromethanesulfonyl)imide anion (TFSI-) tethered to oligoethylene oxide (EO) (EO(12)TFSI-/Li+) were determined and compared to those in a binary solution of the oligoethylene oxide with LiTFSI salt (EO(12)/LiTFSI) by using molecular dynamics (MD) simulations and AC conductivity measurements. The latter revealed that the AC conductivity is 1 to 2 orders of magnitude less in the IL compared to the oligoether/salt binary electrolyte with greater differences being observed at lower temperatures. The conductivity of these electrolytes was accurately predicted by MD simulations, which were used in conjunction with a microscopic model to determine mechanisms of Li+ transport. It was discerned that structure-diffusion of the Li+ cation in the binary electrolyte (EO(12)/LiTFSI-) was similar to that in EO(12)TFSI-/Li+ IL at high temperature (>363 K), thus, one can estimate conductivity of IL at this temperature range if one knows the structure-diffusion of Li+ in the binary electrolyte. However, the rate of structure-diffusion of Li+ in IL was found to slow more dramatically with decreasing temperature than in the binary electrolyte. Lithium motion together with EO(12) solvent accounted for 90% of Li+ transport in EO(12)/LiTFSI-, while the Li+ motion together with the EO(12)TFSI- anion contributed approximately half to the total Li+ transport but did not contribute to the charge transport in IL.  相似文献   

4.
采用Raman光谱、傅里叶转换红外光谱和X-射线衍射光谱研究N-甲基-N-丙基哌啶双三氟甲磺酸亚胺离子液体(PP13TFSI)和双三氟甲磺酸亚胺锂盐(LiTFSI)对PVDF-HFP聚合物聚合方式的影响,结果表明,PP13TFSI、LiTFSI和PVDF-HFP是共混存在的,同时加入PP13TFSI和LiTFSI会使聚合物的聚合方式由晶体结构转变为无定形结构. 通过对电解质及其各组分的线性扫描伏安曲线和热重曲线分析可知,溶剂N-甲基吡咯烷酮(NMP)容易残留在凝胶聚合物电解质(ILGPE)中,这会降低ILGPE的电化学稳定性和热稳定性. 作者对固态LiFePO4|ILGPE|Li电池的倍率性能进行了研究,实验结果表明其具有较好的倍率性能,当电池倍率由C/10增大至2C,然后再回到C/10时,其容量可以恢复到原来的90.9%左右. 该研究结果对理解PP13TFSI和LiTFSI在ILGPE中的作用机理具有重要的意义.  相似文献   

5.
A new kind of polymer electrolyte is prepared from N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP1.3TFSI), polyethylene oxide (PEO), and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI). IR and X-ray diffraction results demonstrate that the addition of ionic liquid decreases the crystallization of PEO. Thermal and electrochemical properties have been tested for the solid polymer electrolytes, the addition of the room temperature molten salt PP1.3TFSI to the conventional P(EO)20LiTFSI polymer electrolyte leads to the improvement of the thermal stability and the ionic conductivity (x = 1.27, 2.06 × 10−4 S cm−1 at room temperature), and the reasonable lithium transference number is also obtained. The Li/LiFePO4 cell using this polymer electrolyte shows promising reversible capacity, 120 mAh g−1 at room temperature and 164 mAh g−1 at 55 °C.  相似文献   

6.
Solid polymer electrolytes (SPEs) are compounds of great interest as safe and flexible alternative ionics materials, particularly suitable for energy storage devices. We study an unusual dependence on the salt concentration of the ionic conductivity in an SPE system based on poly(ethylene carbonate) (PEC). Dielectric relaxation spectroscopy reveals that the ionic conductivity of PEC/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte continues to increase with increasing salt concentration because the segmental motion of the polymer chains is enhanced by the plasticizing effect of the imide anion. Fourier transfer‐infrared (FTIR) spectroscopy suggests that this unusual phenomenon arises because of a relatively loose coordination structure having moderately aggregated ions, in contrast to polyether‐based systems. Comparative FTIR study against PEC/lithium perchlorate (LiClO4) electrolytes suggests that weak ionic interaction between Li and TFSI ions is also important. Highly concentrated electrolytes with both reasonable conductivity and high lithium transference number (t+) can be obtained in the PEC/LiTFSI system as a result of the unusual salt concentration dependence of the conductivity and the ionic solvation structure. The resulting concentrated PEC/LiTFSI electrolytes have extraordinary oxidation stability and prevent any Al corrosion reaction in a cyclic voltammetry. These are inherent effects of the highly concentrated salt. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2442–2447  相似文献   

7.
Self‐standing films of (meth)acrylate‐based polymer gel electrolytes with high ionic liquid content (80 wt %) were prepared by in situ thermally or photo induced radical copolymerization of mono‐functional and di‐functional (meth)acrylates in an ionic liquid in the presence/absence of a lithium salt. Their ionic conductivity, thermal property, mechanical property, and flammability were examined. 1‐Ethyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide (EMImTFSI) or 1‐ethyl‐3‐methylimidazolium bis(fluorosulfonyl)imide (EMImFSI) was used as the ionic liquid, and lithium bis(trifluoromethanesulfonyl)imide LiTFSI was used as the lithium salt. The obtained films were semitransparent and flexible with good to moderate thermal stability and mechanical strength with high ionic conductivity. The EMImFSI‐containing gel electrolytes showed higher ionic conductivity than the corresponding EMImTFSI‐containing gel electrolytes. The ionic conductivity in the acrylate‐based gel electrolytes was slightly increased by addition of lithium salt, while that in the corresponding methacrylate‐based electrolytes was decreased significantly. The flame test showed the ionic liquid containing networked polymer gel electrolytes to have low if any flammability and was therefore confirmed to be highly safe. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

8.
Ionic‐liquid‐containing polymer films were prepared by swelling poly(ethylene glycol)‐based networked polymers having lithium salt structures with an ionic liquid, 1‐ethyl‐3‐methylimidazolium bis(fluorosulfonyl)imide (EMImFSI), or with an EMImFSI solution of lithium bis(trifluoromethanesulfonyl) imide (LiTFSI). Their fundamental physical properties were investigated. The networked polymer films having lithium salt structures were prepared by curing a mixture of poly(ethylene glycol) diglycidyl ether and lithium 3‐glycidyloxypropanesulfonate or lithium 3‐(glycidyloxypropanesulfonyl)(trifluoromethanesulfonyl)imide with poly(ethylene glycol) bis(3‐aminopropyl) terminated. The obtained ionic‐liquid‐containing films were flexible and self‐standing. They showed high ionic conductivity at room temperature, 1.16–2.09 S/m for samples without LiTFSI and 0.29–0.43 S/m for those with 10 wt % LiTFSI. Their thermal decomposition temperature was above 220 °C, and melting temperature of the ionic liquid incorporated in the film was around ?16 °C. They exhibited high safety due to good nonflammability of the ionic liquid. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

9.
《先进技术聚合物》2018,29(2):820-824
We prepared a ternary composite polymer electrolyte from poly(ethylene carbonate) (PEC), lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) and non‐calcined silica nanofibers (SNFs) having 3 average diameters (300, 700, and 1000 nm). The SNF composite electrolytes were obtained as homogeneous, self‐standing membranes. The ionic conductivity of PEC/LiTFSI 100 mol% was increased by the addition of SNFs, and the thinner SNFs with average diameter 300 nm were most effective in improving the conductivity. The conductivity was of the order of 10−4 S/cm at 60°C. The lithium transference number of the SNF300 composite was greater than 0.7. Stress‐strain curves of the composites indicated significant increases in Young's modulus and maximum stress for the PEC electrolytes. The 5% weight‐loss temperature of the composites also improved with the addition of SNF.  相似文献   

10.
New comb polysiloxanes with mixed substituents were synthesized by hydrosilylation of PMHS with 4-allyloxymethyl-[1,3]dioxolan-2-one and tri(ethylene glycol) allyl methyl ether (AMPEO3). The effect of the incorporation of carbonate groups on ionic transport, viscosity and thermal properties has been investigated. When doped with lithium bis(trifluorosulfonyl) imide, LiTFSI, the mixed substituted polysiloxane polymers with varying carbonate content all exhibited conductivity higher than those for the polysiloxanes with pure carbonate or pure oligoethyleneoxy substituents. The maximum ambient conductivity in this series was 1.62× 10−4 S/cm, occurring for the polymer containing 8.5% polar carbonate groups at a doping level of EO/LiTFSI = 15. The impedance measurement results showed that polymers containing larger amounts of carbonate groups exhibited lower conductivity, probably because of their increased viscosity and higher glass transition temperature. The conduction mechanism for these new comb polymers obeys free volume theory, as indicated by conductivity data fit to the VTF equation. We dedicate this paper to Professor Dick Jones, polysilane pioneer and valued friend.  相似文献   

11.
Ionic liquid monomer couples were prepared by the neutralization of 1‐vinylimidazole with vinylsulfonic acid or 3‐sulfopropyl acrylate. These ionic liquid monomer couples were viscous liquid at room temperature and showed low glass transition temperature (Tg) at ?83 °C and ?73 °C, respectively. These monomer couples were copolymerized to prepare ion conductive polymer matrix. Thus prepared ionic liquid copolymers had no carrier ions, and they showed very low ionic conductivity of below 10?9 S cm?1. Equimolar amount of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to imidazolium salt unit was then added to generate carrier ions in the ionic liquid copolymers. Poly(vinylimidazolium‐co‐vinylsulfonate) containing equimolar LiTFSI showed the ionic conductivity of 4 × 10?8 S cm?1 at 30 °C. Advanced copolymer, poly(vinylimidazolium‐co‐3‐sulfopropyl acrylate) which has flexible spacer between the anionic charge and polymer main chain, showed the ionic conductivity of about 10?6 S cm?1 at 30 °C, which is 100 times higher than that of copolymer without spacer. Even an excess amount of LiTFSI was added, the ionic conductivity of the copolymer kept this conductivity. This tendency is completely different from the typical polyether systems. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   

12.
A series of ionic liquids (ILs) are prepared by neutralizing tertiary amines with N,N-bis(trifluoromethanesulfonyl)imide (HTFSI). As demonstrated by thermal and electrochemical characterizations, these ILs have very good temperature stability and a high ionic conductivity, that is, of the order of 10(-2) S cm-1. By incorporating these ILs into a poly(vinylidenfluoride-co-hexafluoropropylene) polymer matrix, membranes with a high melting temperature, high decomposition point and with an ionic conductivity of about 10(-2) S cm-1 at 140 degrees C, are obtained. These IL-based, proton-conducting membranes are proposed as new polymer electrolytes for high-temperature polymer electrolyte membrane fuel cells (PEMFCs).  相似文献   

13.
Molecular dynamics (MD) simulations have been performed on N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (mppy(+)TFSI(-)) and N,N-dimethyl- pyrrolidinium bis(trifluoromethanesulfonyl)imide (mmpy(+)TFSI(+)) ionic liquids (ILs) doped with 0.25 mol fraction LiTFSI salt at 303-500 K. The liquid density, ion self-diffusion coefficients, and conductivity predicted by MD simulations were found to be in good agreement with experimental data, where available. MD simulations reveal that the Li(+) environment is similar in mppy(+)TFSI(-) and mmpy(+)TFSI(+) ILs doped with LiTFSI. The Li(+) cations were found to be coordinated on average by slightly less than four oxygen atoms with each oxygen atom being contributed by a different TFSI(-) anion. Significant lithium aggregation by sharing up to three TFSI(-) anions bridging two lithiums was observed, particularly at lower temperatures where the lithium aggregates were found to be stable for tens of nanoseconds. Polarization of TFSI(-) anions is largely responsible for the formation of such lithium aggregates. Li(+) transport was found to occur primarily by exchange of TFSI(-) anions in the first coordination shell with a smaller (approximately 30%) contribution also due to Li(+) cations diffusing together with their first coordination shell. In both ILs, ion self-diffusion coefficients followed the order Li(+) < TFSI(-) < mmpy(+) or mppy(+) with all ion diffusion in mmpy(+)TFSI(-) being systematically slower than that in mppy(+)TFSI(-). Conductivity due to the Li(+) cation in LiTFSI doped mppy(+)TFSI(-) IL was found to be greater than that for a model poly(ethylene oxide)(PEO)/LiTFSI polymer electrolyte but significantly lower than that for an ethylene carbonate/LiTFSI liquid electrolyte. Finally, the time-dependent shear modulus for the LiTFSI doped ILs was found to be similar to that for a model poly(ethylene oxide)(PEO)/LiTFSI polymer electrolyte on the subnanosecond time scale.  相似文献   

14.
Solid polymer electrolytes (SPE) have been identified as a class of materials which could enable the fabrication of high energy density solid state lithium rechargeable batteries which could meet the performance requirements for advanced portable electronic and automotive applications. In order to achieve this goal, novel SPE systems having high ionic conductivity and good mechanical properties at or near ambient temperature must be developed. Novel lithium salts believed to be useful in realizing this objective have recently been proposed. The thermal behavior of SPE systems based on high molecular weight poly(ethylene oxide) (PEO) and on two novel salts, the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and the lithium tris(trifluoromethylsulfonyl)-methanide (LiTSFM) is reported and compared with the thermal behavior of the high molecular weight PEO–lithium trifluoromethane sulfonate (LiTFLT) SPE system. Phase diagrams for the PEO–LiTFSI and PEO–LiTFSM SPE systems have been established and are discussed in terms of their impact on SPE-based rechargeable lithium battery technologies. The use of a novel plasticizer in conjunction with the PEO–LiTFSI-based SPE system is reported and it is shown how this modifies the thermal behavior of the PEO–LiTFSI SPE system.  相似文献   

15.
The principle motivation of this research work is to develop environmental-friendly polymer electrolytes utilizing corn starch (CS), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1-allyl-3-methylimidazolium chloride ([Amim] Cl) by solution casting technique. The highest ionic conductivity value was achieved for the composition CS:LiTFSI:[Amim] Cl (14 wt. %:6 wt. %:80 wt. %) which exhibits the ionic conductivity value of 5.68 × 10−2 S cm−1 at 40 °C with the activation energy of 4.86 kJ mol−1. This sample possess high concentration of amorphous phase coupled with greater presence of conducting cations (lithium, Li+ and imidazolium, [Amim]+) as depicted by the dielectric loss tangent plot. The conductivity-temperature plots were found to obey Arrhenius rule in which the conductivity mechanism is thermally assisted. The melting temperature of polymer electrolyte decreases with increase in [Amim] Cl content. This is attributed to the good miscibility of [Amim] Cl in CS:LiTFSI matrix inducing structural disorderliness. Reference to the TGA results it is found that the addition of [Amim] Cl diminishes the heat-resistivity whereas enhancement in the thermal stability occurred at the initial addition and declines with further doping of [Amim] Cl.  相似文献   

16.
李雪  龚正良 《电化学》2020,26(3):338
锂硫电池由于具有高的理论比能量引起了广泛关注,然而传统液态锂硫电池由于多硫化物的“穿梭效应”以及安全问题而限制了其应用,全固态锂硫电池可显著提高电池安全性能并有望解决多硫化物的穿梭问题. 本文采用传统的溶液浇铸法制备了具有不同的[EO]/[Li+]的PEO-LiTFSI聚合物电解质,并将其应用于锂硫电池. 研究发现,虽然[EO]/[Li+] = 8的聚合物电解质具有更高的离子电导率,但是[EO]/[Li+] = 20的电解质与金属锂负极间的界面阻抗更低,界面稳定性更好. Li|PEO-LiTFSI([EO]/[Li+]=20)|Li对称电池在60 °C,电流密度为0.1 mA·cm-2时可稳定循环超过300 h,而Li|PEO-LiTFSI ([EO]/[Li+]=8)|Li对称电池循环75 h就出现了短路现象. 基于PEO-LiTFSI([EO]/[Li+]=20)电解质的锂硫电池首圈放电比容量为934 mAh·g-1,循环16圈后放电比容量为917 mAh·g-1以上. 而基于PEO-LiTFSI ([EO]/[Li+]=8)电解质的锂硫电池,由于与锂负极较低的界面稳定性不能够正常循环,首圈就出现了严重过充现象.  相似文献   

17.
Developing high-performance functional polymer-based electrolytes is important for realizing next generation safe lithium metal batteries. In this study, a new type of quasi-solid polymer network electrolyte (SIPH-x-y%) was prepared by combining synthesized polymer network (SIPH) containing urethane bond linked ionic liquids (ILs), polyethylene glycol (PEG), and disulfide bond moieties, lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI), and glyme type additive. It was found that SIPH-20-40% was mechanically flexible, self-healable, and showed high ionic conductivity of 2.67×10−4 S cm−1. Also, SIPH-20-40% possesses a high lithium ion transference number of 0.43 and good electrochemical stability. These properties enabled the SIPH-20-40% electrolyte membrane to support Li/Li symmetrical cell to cycle stably during long term Li plating and stripping. The Li/SIPH-20-40%/LFP showed high delivered specific capacity and good stability (166.1 mAh g−1 after 106 cycles at 0.2 C). Such glyme doped polymer network electrolyte provides new experimental findings for developing polymer-based electrolyte with excellent mechanical integrity and battery related properties.  相似文献   

18.
Ionic liquids (IL) are very promising “solvent-free” electrolytes for high-voltage double-layer supercapacitors (EDLCs) and to this purpose they are generally selected on the basis of their bulk properties, such as electrochemical stability and ion conductivity, without taking into account those of the electrified electrode-IL interface. This interface, which has yet to be well characterized, has features that notably affect electrode capacitance, and our paper for the first time highlights the importance of the molecular chemistry and structure of the ions for the double-layer capacitive response of carbonaceous electrodes in IL. The double-layer capacitive responses of negatively charged electrodes based on activated carbons and aero/cryo/xerogel carbons in two ILs featuring the same anion and different cations of almost the same size, i.e. the N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) and 1-ethyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI) are reported. The porosity, structure and surface chemistry of the carbons are compared to their capacitive response to evince the role played by these carbon properties and by the chemistry and structure of the IL ions in the electric double-layer.  相似文献   

19.
An oligo/poly(methyl(2-(tris(2-H methoxyethoxy)silyl)ethyl)siloxane)), 390EO, and 2550EO, were synthesized. Dilute electrolyte solutions of 390EO and 2550EO were prepared using LiTFSI, LiFSI, and LiPF6. The influence of the length of the siloxane polymer chain, salt type, and Si-tripodand centers at the side chain on ionic conductivity, tLi+, and physical properties were examined. Both electrolyte systems showed high values of tLi+ (0.35 for 2550EO/LiTFSI and 0.64 for 390EO/LiTFSI). Alternatively 390EO/LiPF6 and 2550EO/LiPF6 displayed high tLi+ values of 0.61 and 0.44, respectively, while 390EO/LiFSI displayed the smallest tLi+ (0.25). To clarify the role played by the Li+ environment in Li+ transport, the solvation states of electrolytes were examined. It was observed that anion solvation can be achieved using siloxane-based solvent in all systems. Walden plot analysis demonstrates that ionic diffusion was not controlled by either macroviscosity/microviscosity in the siloxane-based polymer electrolytes. Ions instead move along a relatively smooth ion-pathway without complete full segmental reorientation in 2550EO as a result of decoupling and high ion solvation behavior. Conversely, in 390EO, ions might move to available sites by a jumping after decoupling with low ion solvation behavior. Consequently, a high t Li+ was achieved, and the oxidative stability of the salt was ensured.  相似文献   

20.
《Solid State Sciences》2012,14(5):598-606
Gel polymer electrolytes containing 1-ethyl-3-methylimidazolium-bis (trifluoromethyl-sulfnyl)imide (EMITFSI) ionic liquid were prepared for lithium ion batteries by solution casting method. Thermal and electrochemical properties have been determined for the gel polymer electrolytes. Proper addition of EMITFSI to the P(VdF-HFP)-LiTFSI polymer electrolyte improves the ionic conductivity and electrochemical window to 2.11 × 10−3 S cm−1 (30 °C) and 4.6 V. In combination of the prepared ternary P(VdF-HFP)-LiTFSI-EMITFSI ionic liquid polymer electrolytes, Li4Ti5O12 anode exhibited two extra voltage plateaus around 1.1 V and 2.3 V except the typical voltage plateau around 1.6 V by possible side reaction between ionic liquid and polymer. LiFePO4 cathode exhibited high capacity above 140 mA h g−1 and retention of 93.1% due to the suppressed polarization effect caused by enhanced ion transport properties. The high temperature of 80 °C didn't have significant impact on the cycling performance.  相似文献   

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