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1.
Quaternary plasticized solid polymer electrolyte (SPE) films composed of poly(ethylene oxide), LiClO4, Li1.3Al0.3Ti1.7(PO4)3, and either ethylene carbonate or propylene carbonate as plasticizer (over a range of 10–40 wt%) were prepared by a solution‐cast technique. X‐ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) indicated that components such as LiClO4 and Li1.3Al0.3Ti1.7(PO4)3 and the plasticizers exerted important effects on the plasticized quaternary SPE systems. XRD analysis revealed the influence from each component on the crystalline phase. DSC results demonstrated the greater flexibility of the polymer chains, which favored ionic conduction. SEM examination revealed the smooth and homogeneous surface morphology of the plasticized polymer electrolyte films. EIS suggested that the temperature dependence of the films' ionic conductivity obeyed the Vogel–Tamman–Fulcher (VTF) relation, and that the segmental movement of the polymer chains was closely related to ionic conduction with increasing temperature. The pre‐exponential factor and pseudo activation energy both increased with increasing plasticizer content and were maximized at 40 wt% plasticizer content. The charge transport in all polymer electrolyte films was predominantly reliant on lithium ions. All transference numbers were less than 0.5. Copyright © 2006 Society of Chemical Industry 相似文献
2.
Tetramethoxysilane (TMOS) or tetraethoxysilane (TEOS), an organic monomer [methylmethacrylate (MMA) or styrene (St)] and either α‐propylmethacryloxy‐ω‐trimethylsiloxy‐oligo(dimethylsiloxane) (OMS), as a compatibilizing agent, or α,ω‐bis(vinyl) oligo(dimethylsiloxane) (OVS), as compatibilizing and crosslinking agent, were allowed to undergo a sol–gel reaction under acidic condition and in the presence of 2,2′‐azoisobutyronitrile (AIBN) as a free‐radical initiator. The hydrolysis‐condensation and in situ free‐radical polymerization occur independently, to give a hybrid consisting of both inorganic and organic components. The conversion of the monomers to the proper polymers was monitored by IR spectroscopy and TGA. The resistance of the organic polymers to solvent extraction was also studied. The hybrids were pyrolyzed in an oxidative atmosphere. By decomposition, the organic polymer generated pores in the inorganic matrix. A quantitative evaluation of the characteristics for the resulting porous material was made by determination of the specific area, pore volume, and average radius. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2060–2067, 2003 相似文献
3.
The transparent and flexible solid polymer electrolytes (SPEs) were fabricated from polyacrylonitrile‐polyethylene oxide (PAN‐PEO) copolymer which was synthesized by methacrylate‐headed PEO macromonomer and acrylonitrile. The formation of copolymer is confirmed by Fourier‐transform infrared spectroscopy (FTIR) measurements. The ionic conductivity was measured by alternating current (AC) impedance spectroscopy. Ionic conductivity of PAN‐PEO‐LiClO4 complexes was investigated with various salt concentration, temperatures and molecular weight of PEO (Mn). And the maximum ionic conductivity at room temperature was measured to be 3.54 × 10?4 S/cm with an [Li+]/[EO] mole ratio of about 0.1. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 461–464, 2006 相似文献
4.
Weihua Zhu Bing Yang Xinling Wang Lei Wang Xiaozhen Tang Changzheng Yang 《应用聚合物科学杂志》2002,83(1):103-111
A series of polyurethanes (PUs) with different polyether soft segments [polydioxolane (PDXL), polyethylene glycol (PEG), or PDXL/PEG] were synthesized successfully, and solid polymer electrolytes based on PU/LiClO4 complexes were prepared. The relations between structure and the ionic conductive properties of the PU‐based electrolytes were investigated by means of Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, and complex impedance analysis. Results showed that the glass‐transition temperature (Tg) of PDXL–PU was lower than that of PEG–PU. Doped lithium perchlorate (LiClO4) salt could be dissolved well in soft segments of PDXL–PU. The ionic conductivity of the PDXL–PU/LiClO4 complex could reach a value of 2 × 10?5 S/cm at room temperature without the addition of an organic plasticizer. The system with PDXL/PEG as a soft segment had a higher Tg and a lower ionic conductivity than the one with PDXL as a soft segment. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 103–111, 2002 相似文献
5.
To study the effect of the silica content on the properties of the salt‐free and salt‐added hybrids based on poly(ethylene oxide) (PEO) and silica, two series of hybrids, PEO–silica and PEO–silica–LiClO4 (O:Li, 9:1) hybrids were prepared via the in situ acid‐catalyzed sol–gel reactions of the precursors [i.e., PEO functionalized with triethoxysilane and tetraethyl orthosilicate (TEOS)]. The morphology of the hybrids was examined by scanning electron microscopy (SEM) of the fracture surfaces of the hybrid. The results indicated that the discontinuity develops with increasing the weight percent of silica in both hybrids. The differential scanning calorimetric (DSC) analysis indicated that effects of silica content on the glass transition temperatures (Tg) of the PEO phase were different in salt‐free and salt‐added hybrids. The Tg of PEO phase increased with increasing weight percent of silica in salt‐free hybrids, whereas the curve of Tg of PEO phase and silica content had a maximum at 35 wt % of silica content in salt‐added hybrids. For both salt‐free and salt‐added hybrids, peaks of the loss tangent, determined by dynamic mechanical analysis (DMA) were gradually broadened and lowered with increasing weight percent of silica. The storage modulus, E′, in the region above Tg increases with increasing silica content for both PEO–silica and PEO–silica–LiClO4 hybrids. In the conductivity and composition curves for PEO–silica–LiClO4 hybrids, the conductivity shows a maximum value of 3.7 × 10?6 S/cm, corresponding to the sample with a 35 wt % of silica. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2471–2479, 2001 相似文献
6.
The organic–inorganic hybrid material poly(styrene‐methyl methacrylate)‐silica (P(St‐MMA )‐SiO2) was successfully prepared by in situ polymerization confirmed by Fourier transform infrared spectroscopy and was employed to fabricate poly(vinylidene fluoride‐hexafluoropropylene) (P(VDF‐HFP )) based composite polymer electrolyte (CPE ) membrane. Desirable CPEs can be obtained by immersing the CPE membranes into 1.0 mol L?1 LiPF6‐EC /DMC /EMC (LiPF6 ethylene carbonate + dimethyl carbonate + ethylmethyl carbonate) liquid electrolyte for about 0.5 h for activation. The corresponding physicochemical properties were characterized by SEM , XRD , electrochemical impedance spectroscopy and charge–discharge cycle testing measurements. The results indicate that the as‐prepared CPEs have excellent properties when the mass ratio of the hybrid P(St‐MMA )‐SiO 2 particles to polymer matrix P(VDF‐HFP ) reaches 1:10, at which point the SEM analyses show that the as‐prepared P(St‐MMA )‐SiO 2 particles are uniformly dispersed in the membrane and the CPE membrane presents a homogeneous surface with abundant interconnected micropores. The XRD results show that there may exist interaction forces between the P(St‐MMA )‐SiO 2 particles and the polymer matrix, which can obviously decrease the crystallinity of the composite membrane. Moreover, the ionic conductivity at room temperature and the electrochemical working window of the CPE membrane can reach 3.146 mS cm?1 and 4.7 V, respectively. The assembled LiCoO2/CPE /Li coin cell with the CPE presents excellent charge–discharge and C ‐rate performance, which indicates that P(St‐MMA )‐SiO 2 hybrid material is a promising additive for the P(VDF‐HFP ) based CPE of the lithium ion battery. © 2016 Society of Chemical Industry 相似文献
7.
Xiahong Zhang Jianwen Yang Zhaohua Zeng Liang Huang Yonglie Chen Haihua Wang 《Polymer International》2006,55(4):466-472
Organic–inorganic hybrid UV‐curable coatings were synthesized through blending UV‐curable components and stabilized titania sol prepared via a sol–gel process of tetrabutyl titanate (TBT) with three different stabilizers, acetylacetone (Acac), isopropyl tri(dioctyl)pyrophosphato titanate coupling agent (TTPO) and a polymerizable organic phosphoric acid (MAP). The size and the dispersion of titania particle in the UV‐cured organic matrix were dominated by the properties of these stabilizers. A cured hybrid film with titania particle size around 20 nm was obtained when TTPO was utilized as protection agent for the sol. It is interesting that the hardness and flexibility of the photocured hybrid films were improved simultaneously, in contrast to results with neat organic UV‐curable formulations. Copyright © 2006 Society of Chemical Industry 相似文献
8.
A new class of ionic conducting organic/inorganic hybrid composite electrolyte with high conductivity, better electrochemical stability and mechanical behavior was prepared through the sol–gel processing between ethylene‐bridged polysilsesquioxane and poly(ethylene glycol) (PEG). The composite electrolyte with 0.05 LiClO4 per PEG repeat unit has the best conductivity up to 10?4 S/cm at room temperature with the transference number up to 0.48 and an electrochemical stability window as high as 5.5 V versus Li/Li+. Moreover, the effect of the PEG chain length on the properties of the composite electrolyte has also been studied. The interactions between ions and polymer have also been investigated for the composite electrolyte in the presence of LiClO4 by means of FTIR, DSC, and TGA. The results indicated the interaction of Li+ ions with the ether oxygen of the PEG, and the formation of transient crosslinking with LiClO4, resulting in an increase of the Tg of the composite electrolyte. The VTF‐type behavior of the ionic conductivity implied that the diffusion of the charge carriers was assisted by the segmental motions of the polymer chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2752–2758, 2007 相似文献
9.
Sevim Karata Zuhal Hogr Yusuf Mencelolu Nilhan Kayaman‐Apohan Atilla Güngr 《应用聚合物科学杂志》2006,102(2):1906-1914
UV‐curable, organic–inorganic hybrid materials were synthesized via sol–gel reactions for tetraethylorthosilicate, and methacryloxypropyl trimethoxysilane in the presence of the acrylated phenylphosphine oxide resin (APPO) and a bisphenol‐A‐based epoxy acrylate resin. The sol–gel precursor content in the hybrid coatings was varied from 0 to 30 wt %. The adhesion, flexibility, and hardness of the coatings were characterized. The influences of the amounts of inorganic component incorporated into the coatings were studied. Results from the mechanical measurements show that the properties of hybrid coatings improve with the increase in sol–gel precursor content. In addition, thermal properties of the hybrids were studied by thermogravimetric analysis in air atmosphere. The char yield of pure organic coating was 32% and that of 30 wt % silicate containing hybrid coating was 30% at 500°C in air atmosphere. This result demonstrates the pronounced effect of APPO on the flame retardance of coatings. Gas chromatography/mass spectrometry analyses showed that the initial weight loss obtained in thermogravimetric analysis is due to the degradation products of the photoinitator and the reactive diluent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1906–1914, 2006 相似文献
10.
The main thermodynamic parameters were evaluated for the dextran/methoxy ethylene glycol (MEG) system by viscosity measurements at 25, 30, 35, 40, and 45°C. The long-range and short-range interaction parameters were determined by extrapolation methods, i.e, Kurata-Stockmayer-Fixman, Berry, and Inagaki-Suzuki-Kurata equations. Calculated values, as well as the unperturbed root-mean-square end-to-end distance and hydrodynamic expansion factor, were interpreted mainly on the basis of hydrogen-bond formation between polymer segments and dextran/MEG molecules in solution. The thermodynamic interaction parameter was also evaluated for the same system. The theta temperatures were obtained from the temperature dependence of the interaction parameter, dependence of (1/2-χ) and the second virial coefficient in the temperature interval of 25 and 45°C for the system and quite a good accordance was indicated with the calculated values evaluated via extrapolation and interpolation methods. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 948–953, 2001 相似文献
11.
Novel dendrimer‐silica gel hybrids were prepared from amino‐terminated poly(amidoamine) generation 3 (32 cascade) and its partly ester‐terminated derivatives with tetraethoxysilane in the presence of a coupling agent 3‐glycidoxypropyltrimethoxysilane by in situ sol‐gel process. The scanning electron micrograph spectra showed that these transparent hybrids have the nanocomposite structure. Their transparent and thermal properties were characterized by ultraviolet, thermogravimetric analysis. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2186–2190, 2000 相似文献
12.
Alkaline PVA polymer electrolyte with high ionic conductivity of about 0.047 S cm–1 at room temperature was obtained by a solution casting method. The PVA polymer electrolytes, blended with KOH and H2O, were studied by DSC, TGA, cyclic voltammetric and a.c. impedance methods. The PVA polymer electrolytes show good mechanical strength and high ionic conductivity. The electrochemical stability window at the metal–electrolyte interface is ±1.2 V for stainless steel. Ni–MH and Zn–air batteries with PVA polymer electrolytes were assembled and tested. Experimental results show good electrochemical performances of the PVA-based Ni–MH and Zn–air batteries. 相似文献
13.
New organic–inorganic hybrids SiGCX (X = 1 to 3) were prepared from the biopolymer chitosan with a degree of the deacetylation of 86% and three distinct silylating agents of the type (CH3O)3Si R NH2 [R = (CH2)3 , (CH2)3NH(CH2)2 and (CH2)3NH(CH2)2NH(CH2)2 ]. Both chitosan and silylating agents have the amine groups crosslinking through linear glutaraldehyde units. Two stages were proposed for this synthetic method: crosslinking, and sol‐gel processes. The resulting dried hydrogels are amorphous, insoluble in organic as well as acidic or alkaline aqueous media, and exhibited a lamellae‐like surface morphology. The hybrids SiGCX (X = 2 and 3) have a larger adsorption capacity for copper ion than natural chitosan, with very similar kinetics of adsorption, defining a plateau after 1 h. The adsorption of copper increases with the organic chain length of the silylating agents: [(1.72 ± 0.05); (1.98 ± 0.06) and (2.49 ± 0.07)] × 10−2 mmol/g for SiGCX (X = 1 to 3), respectively, and chitosan adsorbed (1.72 ± 0.05) × 10−2 mmol/g. These hybrids presented a good capacity for immobilizing enzymes, which decreased with the increase of the organic chain length of the silylating agents, that is, from SiGC3 to SiGC1. The amount of catalase immobilized for the hybrids SIGCX (X = 1 to 3) is 29.03 ± 0.87; 25.79 ± 0.77, and 17.94 ± 0.54 mg g−1, respectively, which is larger than the value of 12.21 ± 0.37 mg g−1 obtained for chitosan. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 797–804, 2000 相似文献
14.
Silica–polyimide hybrid composites were prepared via a sol–gel process and thermal imidization. Two different types of soluble precursors, poly(amic acid) (PAA) and poly(amic diethyl ester) (ES), chemically convertible to poly(p-phenylene biphenyltetracarboximide), were used as organic polymer matrix component, and tetraethoxysilane (TEOS), convertible to silica, as the inorganic component. The structure of composites prepared as thin films was investigated by means of small-angle X-ray scattering, scanning electron microscopy and atomic force microscopy. Nanometre-scale composites were successfully obtained for ≤30wt% TEOS-loaded mixtures with ES and PAA. It was considered from the microstructural investigation that the composite films based on ES were not significantly affected by the inorganic particles generated, maintaining the structure of the homopolyimide, while those based on PAA did not preserve the structure due to the nanoparticles grown in situ during the sol–gel process. © 1997 SCI. 相似文献
15.
Three nonelectrolyte samples and one gel polymer electrolyte sample were prepared from poly(vinylidene fluoride) (PVDF), propylene glycol carbonate (PC), and LiClO4 in the present article. Fourier transform infrared spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, and scanning electron microscopy were used to study morphology structure of all the samples. Results showed that there were great interactions among PVDF, PC, and lithium salt, which led to different morphology properties of different samples. Interactions between PVDF and PC mainly occurred on the surface area of PVDF crystalline, while interactions between PC, PVDF, and lithium salt mainly occurred in the amorphous area. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3839–3842, 2004 相似文献
16.
R. Baskaran S. Selvasekarapandian N. Kuwata Yoshiki Iwai J. Kawamura T. Hattori 《应用聚合物科学杂志》2008,110(4):1945-1954
The lithium‐ion conducting gel polymer electrolytes (GPE), PVAc‐DMF‐LiClO4 of various compositions have been prepared by solution casting technique. 1H NMR results reveal the existence of DMF in the gel polymer electrolytes at ambient temperature. Structure and surface morphology characterization have been studied by X‐ray diffraction analysis (XRD) and scanning electron microscopy (SEM) measurements. Thermal and conductivity behavior of polymer‐ and plasticizer‐salt complexes have been studied by differential scanning calorimetry (DSC), TG/DTA, and impedance spectroscopy results. XRD and SEM analyses indicate the amorphous nature of the gel polymer‐salt complex. DSC measurements show a decrease in Tg with the increase in DMF concentrations. The thermal stability of the PVAc : DMF : LiClO4 gel polymer electrolytes has been found to be in the range of (30–60°C). The dc conductivity of gel polymer electrolytes, obtained from impedance spectra, has been found to vary between 7.6 × 10?7 and 4.1 × 10?4 S cm?1 at 303 K depending on the concentration of DMF (10–20 wt %) in the polymer electrolytes. The temperature dependence of conductivity of the polymer electrolyte complexes appears to obey the VTF behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
17.
With the aim of developing ion‐conducting solid polymer electrolytes that combine high ionic conductivity with good mechanical properties, we prepared and investigated nanocomposites of LiClO4‐doped ethylene oxide‐epichlorohydrin (EO‐EPI) copolymers and nanoscale cellulose whiskers derived from tunicates. We show that homogeneous nanocomposite films based on EO‐EPI copolymers, LiClO4, and tunicate whiskers can be produced by solution‐casting THF/water mixtures comprising these components and subsequent compression‐molding. The Young's moduli of the nanocomposites thus produced are increased by a factor of up to >50, when compared to the copolymers, whereas the electrical conductivities experience only comparably small reductions upon introduction of the whiskers. The nanocomposite with the best combination of conductivity (1.6 × 10?4 S/cm at room temperature and a relative humidity of 75%) and Young's modulus (7 MPa) was obtained with a copolymer having an EO‐EPI ratio of 84 : 16, a whisker content of 10% w/w, and a LiClO4 concentration of 5.8% w/w. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2883–2888, 2004 相似文献
18.
The transparent hybrid material, HLP/SiO2, was prepared by an in situ sol–gel process of tetraethoxysilane (TEOS) at 30°C in the presence of hydroxy‐containing linear polyester (HLP) obtained by ring‐opening reaction of diglycidyl ether of bisphenol A (DGEBA) with adipic acid under the catalyzation of triphenylphosphine (TPP). The hetero‐associated hydrogen bonds between the HLP and the residual silanol of silica in the hybrids were investigated by FTIR spectroscopy. Upon heating the hybrid, the interfacial force between the HLP matrix and the silica network changed from hydrogen bonds into covalent Si—O—C bonds through dehydration of hydroxy groups in HLP with residual silanol groups in the silica network. The existence of covalent Si—O—C bonds was proved by solid‐state 29Si‐NMR spectra. Other properties such as tensile strength, glass transition temperature (Tg ), solubility, and thermal stability of the hybrids before and after heat treatment were studied in detail. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1179–1190, 2000 相似文献
19.
Using the copolymer of acrylonitrile (AN), methyl methacrylate (MMA), and poly(ethylene glycol) methyl ether methacrylate as a backbone and poly(ethylene glycol) methyl ether (PEGME) with 1100 molecular weight as side chains, comb‐like gel polymers and their Li salt complexes were synthesized. The dynamic mechanical properties and conductivities were investigated. Results showed that the gel copolymer electrolytes possess two glass transitions: α‐transition and β‐transition. Based on the time–temperature equivalence principle, a master curve was constructed by selecting Tα as reference temperature. By reference to T0 = 50°C, the relation between log τc and c was found to be linear. The master curves are displaced progressively to higher frequencies as the content of plasticizer is increased. The relation between log τp and the content of plasticizer is also linear. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 576–584, 2007 相似文献
20.
In this article, we report on an approach of using an emulsion polymerized polymer in preparing organic–inorganic nanocomposites through a sol–gel technique. By mixing a polymer emulsion with prehydrolyzed tetraethoxysilane transparent poly(butyl methacrylate)/SiO2, nanocomposites were prepared as shown by TEM. AFM, FTIR, and XPS results show that there is a strong interaction between polymer latex particles and the SiO2 network. Comparison of the emulsion method with a traditional solution method shows that nanocomposites can be prepared by both methods, but there is some difference in their morphology and properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 446–454, 2002 相似文献