水铝英石/PEO/LiClO4复合固态聚合物电解质中组分相互作用对PEO结晶的影响

为解决现有锂离子电池的安全性问题,固态电解质的研究备受关注。以Na2SiO3和AlCl3·6H2O为原料,采用溶胶-凝胶法制备出水铝英石(AL);通过溶液共混法将其与聚环氧乙烷/高氯酸锂(PEO/LiClO4)复合得到复合固态聚合物电解质。利用X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、差示扫描量热分析仪(DSC)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)以及光学显微镜(OM)对样品进行结构分析及形貌表征。结果表明:水铝英石和LiClO4与PEO间的非价键力相互作用(络合、氢键及Lewis酸-碱作用)显著抑制PEO的结晶。随着水铝英石含量的增加,PEO的结晶度呈现出先降低后增加的趋势;而随着锂盐含量的增加,PEO的结晶度持续降低,当EO/Li+摩尔比为10∶1,水铝英石的含量为5%(质量分数)时,复合固态聚合物电解质的结晶度最低,仅为4.12%。     

End-functional silicone coupling agent modified PEO/P(VDF-HFP)/SiO(2) nanocomposite polymer electrolyte DSSC

The end-functional silicone coupling agent (dodecyl-trimethoxysilane, DTMS for short) was used to modify the PEO/P(VDF-HFP)/SiO(2) nanocomposite polymer electrolyte (CPE) and the different amounts of DTMS modification effects were studied. The experiments showed the silicone coupling agent with hydrophobic alkyl chains (-C(12)H(25)) chemically engineered on the SiO(2) nanoparticles, and formed a Si-O-Si cross-linked network in the new nanocomposite polymer electrolyte. Proper content of DTMS modified CPE exhibited improved ionic conductivity and the connection with the photoanode and counter electrode. However, much higher content of the DTMS modification changed the conformation of the polymer network and reduced the ionic movement. Compared with the performance (3.84%) of the original DSSC, the DSSC with functional silicone coupling agent modified CPE (DTMS:SiO(2) = 2:1, mol ratio) exhibited improved J(sc) (7.94?mA?cm(-2)), V(oc) (0.624?V) and optimal efficiency (5.2%) (measured at AM1.5, light intensity of 58.4?mW?cm(-2)). The V(oc) of the silicone coupling agent modified polymer electrolyte DSSC is obviously improved, which is mainly due to that the hydrophobic alkyl chain end groups formed an insulating layer that retarded the electron recombination at the TiO(2) nanoporous photoanode/polymer electrolyte interface. The DTMS:SiO(2) = 2:1 modified CPE type DSSC exhibited a performance of 6.42% at a light intensity of 32.1?mW?cm(-2) and 4.94% at 99.2?mW?cm(-2).     

PEO/LiClO4复合体系中PEO的等温结晶动力学研究

用差示扫描量热法研究了聚氧化乙烯(PEO)和PEO/LiClO4复合体系中PEO的等温结晶过程.用Avrami方程分析了PEO和复合体系中PEO的等温结晶动力学,得到PEO在不同体系中等温结晶时的动力学参数.PEO的Avrami指数n都趋近2.5,说明PEO晶体以三维方式依热成核生长.动力学参数表明,复合体系中的PEO以异相成核为主.LiClO4对PEO等温结晶过程的影响为:作为PEO结晶的成核剂而加快其结晶过程;增加了复合体系的粘度,缩短了PEO的半结晶时间,使其结晶总速率增大;降低了复合体系中PEO的绝对结晶度.PEO和复合体系中的PEO等温结晶时成核和生长活化能△E分别为59.28kJ/mol、70.85kJ/mol.     

Impact of ethylene carbonate on ion transport characteristics of PVdF-AgCF3SO3 polymer electrolyte system

The ionic transport in thin film plasticized polymer electrolytes based on polyvinylidene fluoride (PVdF) as the polymer host, silver triflate (AgCF₃SO₃) as salt and ethylene carbonate (EC) as plasticizer prepared by solution casting technique has been reported. Addition of silver triflate has resulted in an increase in the room temperature (298 K) electrical conductivity of the polymer from 10⁻⁶ to 10⁻⁵ S cm⁻¹ whereas incorporation of EC as the plasticizer has further enhanced the conductivity value by an order of magnitude to 10⁻⁴ S cm⁻¹ owing to the possible decrease in crystallinity of the polymer matrix as revealed by the detailed temperature-dependent complex impedance, silver ionic transference number, Fourier transform infrared and X-ray diffraction measurements.     

Electric-magnetic field-induced aligned electrospun poly (ethylene oxide) (PEO) nanofibers

In this work, we report our attempt on the production of well-aligned nanofibers of poly (ethylene oxide) (PEO) by the introduction of magnetic field in the electric field by placing a cylindrical magnet within the electric field. Well-aligned nanofibers were obtained on top of the magnet. No particular structure could be associated with the other sides of the magnet. The aligned nanofibers were characterized by a host of characterization techniques such as optical and scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The diameter of the PEO nanofibers ranged between 500 and 1000 nm.     

Influence of 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulfonyl) imide plasticization on zinc-ion conducting PEO/PVdF blend gel polymer electrolyte

The influence in terms of plasticizer on zinc-ion conducting polymer blend electrolyte system, [PEO (90 wt%)/PVdF (10 wt%)]-15 wt% Zn (CF₃SO₃)₂] with various concentrations of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMIMTFSI) was investigated. The freshly-prepared thin films of [PEO (90 wt%)/PVdF (10 wt%)]-15 wt% Zn (CF₃SO₃)₂)?+?x wt% EMIMTFSI, where x?=?1, 3, 5, 7, and 10 wt%] were characterized by means of X-ray diffraction (XRD), Fourier transformed infrared (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and impedance analysis techniques. The room temperature XRD patterns tend to support the enhanced amorphous phase as a result of deducing the degree of crystallinity of the polymer blend–salt system by the addition of 7 wt% EMIMTFSI. The relevant SEM images of 7 wt% EMIMTFSI incorporated gel polymer electrolyte exhibit a minimised spheurilite structure when compared to that of the polymer blend–salt system. Unusually, the highest ionic conductivity realized in the case of the typical gel polymer electrolyte system, [PEO/PVdF-Zn (CF₃SO₃)₂ + 7 wt% EMIMTFSI] is found to be 1.63?×?10^?4 S cm^?1 at room temperature. The temperature dependence of conductivity has been examined based on the Vogel–Tammann–Fulcher (VTF) equation, thereby suggesting the segmental chain motion and free volume changes. The occurrence of ion dynamics and dielectric relaxation behaviour in the chosen system has been analysed in a detailed fashion at room temperature using frequency response impedance formalisms involving electric modulus and dielectric permittivity features.     

Proton conducting polymer electrolyte: II poly ethylene oxide + NH4l system

A new proton conducting polymer electrolyte PEO + NH₄l system has been investigated. The solution-cast films of different stochiometric ratios have been prepared and characterized. Proton transport has been established using various experimental studies, namely optical microscopy, X-ray diffraction, differential thermal analysis, infrared, coulometry transient ionic current and electrical conductivity measurements at different temperatures and humidity. The maximum conductivity of the complexed material has been found to be 10^–5 S cm^–1. Both H⁺ ion and I^– anion movements are involved with respective transference numbers and mobilities ast _H+=0.74, ,t _l–=0.09, _H+=4.97 × 10^–6 cm² V^–1 s^–1 and _l–=7.65.     

Synthesis and characterization of conjugated poly (amino benzyl alcohol) and poly (ethylene glycol) for solid polymer electrolyte

A solid polymer electrolyte chemically bonded to a π-conjugated polymer was prepared for the use as a designed ladder-type structure by the graft copolymerization of poly (aminobenzyl alcohol) (PABA) with poly (ethylene glycol) (PEG). PABA was used as the frame for the ladder and the PEG as the rungs. The expected synergic effect afforded by the introduction of the ionic salts into the crosslinked conjugated polymer and PEG network was investigated as a function of its structure, morphology, and ionic conductivity. The insertion of the ionic salts into the PABA-PEG-PABA network led to the enhancement of the ionic conductivity compared to that of PEG/LiClO₄. The synergic effect may be explained by the more efficient segmental motion of the polymer chains or better ion mobility in the network due to the interrupted crystallization of the PEG chains. The fine tuning of the crosslinked conjugated polymer gel might enable it to show a faster response to electrochemical stimuli.     

Nanocomposite Films of MoO3 Xerogel with Poly (ethylene oxide) (PEO) Intercalation

(PEO)(x)MoO3.nH(2)O(x=0 similar to2) nanocomposite films were prepared by ion exchange method and polymer solution direct intercalation in sol-gel route. The synthesis and structure of the films were investigated by XRD, DSC, FTIR, etc. The results show that MoO3 xerogel has a layered structure, which arranges in b-direction. The interlayer distance Of MoO3 xerogel increases from 0.690 nm at x=0 to 1.308 nm at x=2 after heat treatment. PEO can be completely intercalated into the interlayer at x=0.5 similar to1 and has strong interaction with MoO3 host.     

An acrylate-based quasi-solid polymer electrolyte incorporating a novel dinitrile poly(ethylene glycol) plasticizer for lithium-ion batteries

Journal of Materials Science - The performance of solid polymer electrolytes is characterized by lower ionic conductivity than conventional liquid electrolytes but provides advantages in terms of...     

Enhancement of ionic conductivity of PEO based polymer electrolyte by the addition of nanosize ceramic powders

The ionic conductivity of polyethylene oxide (PEO) based solid polymer electrolytes (SPEs) has been improved by the addition of nanosize ceramic powders (TiO2 and AL2O3). The PEO based solid polymer electrolytes were prepared by the solution-casting method. Electrochemical measurement shows that the 10 wt% TiO2 PEO-LiClO4 polymer electrolyte has the best ionic conductivity (about 10(-4) S cm(-1) at 40-60 degrees C). The lithium transference number of the 10 wt% TiO2 PEO-LiClO4 polymer electrolyte was measured to be 0.47, which is much higher than that of bare PEO polymer electrolyte. Ac impedance testing shows that the interface resistance of ceramic-added PEO polymer electrolyte is stable. Linear sweep voltammetry measurement shows that the PEO polymer electrolytes are electrochemically stable in the voltage range of 2.0-5.0 V versus a Li/Li+ reference electrode.     

无定型PEO聚合物的合成及导电性能研究

利用低分子量PEG(Mn=400)合成了高分子量的聚氧化乙烯(PEO)嵌段聚合物。采用电化学方法——电渗析除尽了经常规方法(吸附、过滤、沉淀等)所不能除尽的微量杂质,得到纯化产物。通过GPC测得其平均分子量可达105。XRD和1HNMR表明其结构是以[CH2O(CH2CH2O)n]为重复单元的无定型聚合物,其与LiClO4络合物通过10％SiO2纳米材料补强后的固态电解质成膜性和导电性均良好。在测量温度范围内,电导率随温度的变化遵循Arrhenius关系式,22℃时Li+电导率达3.27×10-5 S/cm。     

Effect of ZnO nanoparticles on the structure and ionic relaxation of poly(ethylene oxide)-LiI polymer electrolyte nanocomposites

The effect of ZnO nanoparticles on the structure and ionic relaxation of LiI salt doped poly(ethylene oxide) (PEO) polymer electrolytes has been investigated. X-ray diffraction, high resolution transmission electron microscopy and field emission scanning electron microscopy show that ZnO nanoparticles dispersed in the PEO-LiI polymer electrolyte reduce the crystallinity of PEO and increase relative smoothness of the surface morphology of the nanocomposite electrolyte. The electrical conductivity of the nanocomposites is found to increase due to incorporation of ZnO nanoparticles. We have shown that the structural modification due to insertion of ZnO nanoparticles results in the enhancement of the mobility i.e., the hopping rate of mobile Li+ ions and hence the ionic conductivity of PEO-LiI-ZnO nanocomposite electrolyte.     

Ionic conductivity of a gel polymer electrolyte based on Mg(ClO4)2 and polyacrylonitrile (PAN)

Magnesium ion containing gel polymer electrolytes based on polyacrylonitrile (PAN) have been synthesized and characterized using ac impedance measurements. The electrolyte composition having the highest room temperature conductivity was found by varying the ratios propylene carbonate/ethylene carbonate (PC/EC) and PAN/Mg(ClO₄)₂. The corresponding composition was 18 mol% PAN:64 mol% EC:14 mol% PC:4 mol% Mg(ClO₄)₂. The ac conductivity measurements were carried out from room temperature upto 70 °C with blocking (stainless steel) electrodes. The room temperature conductivity is 3.2×10⁻³ S cm⁻¹ and the activation energy is 0.24 eV over the temperature range used. The high conductivity and the low activation energy of the material could possibly be due to the liquid electrolyte, Mg(ClO₄)₂ in EC/PC trapped in a matrix of PAN, as suggested by previous workers. According to dc polarization measurements, the gel electrolyte appears to be predominantly an anionic conductor.     

原位复合法制备TiO2 / ( PEO)8LiClO4 聚合物电解质

以聚氧化乙烯/ 高氯酸锂络合物( ( PEO)₈LiClO₄ ) 为基体, 通过钛酸四丁酯的水解缩合反应在基体中原位生成TiO₂粒子, 制备了TiO₂ / ( PEO)₈LiClO₄复合聚合物电解质膜。采用SEM、DSC 和交流阻抗方法分别研究了电解质膜的表面形貌、热性能和离子导电性能。结果表明, 原位生成的TiO₂ 粒子均匀分散于PEO 基体中。复合TiO₂后电解质膜的玻璃化转变温度和结晶度降低。电解质膜的离子导电行为满足Arrhenius 方程, 并在5 %TiO₂含量时体系的电导率出现最大值5. 5 ×10 -5 S/ cm (20 ℃) 。以此膜为电解质组装的全固态聚合物锂电池放电时电压平稳, 20 次循环后放电容量保持在107 mAh/ g。      

Conductivity studies on poly(methyl methacrylate)–Li2SO4 polymer electrolyte systems

Thin-film ion-conducting polymer electrolytes based on poly(methyl methacrylate) (PMMA) complexed with Li₂SO₄ have been prepared using the solution casting technique. The complexation of salt with PMMA was confirmed by structural and thermal studies. The results of the electrical conductivity measurements in these electrolytes are reported. A Vogel–Tammann–Fulcher-like temperature dependence of ionic conductivity implies coupling of the ion movement with the segmental motion of the polymer chains in the cross-linked environment. Predominant formation of contact ion pairs of Li₂SO₄ has been consistently observed through conductivity, X-ray diffraction, Fourier transformation and thermal analysis studies.     

基于OMMT/PVDF-HFP的锂离子电池用复合聚合物电解质

对蒙脱石进行改性,并用直接挥发溶剂法制备有机蒙脱石/聚偏氟乙烯-六氟丙烯复合聚合物电解质。用扫描电子显微镜和X射线衍射等对所制电解质性能进行表征,用交流阻抗和充放电实验研究聚合物电池的电化学性质。结果表明：直接挥发溶剂法制得的复合聚合物膜呈蜂窝状,孔穴丰富,强度增加,浸取电解液后室温离子电导率为1.51 mS/cm,电化学稳定窗口为5.5V;以LiCoO₂为正极制得的聚合物电池0.1C充放电,50次循环后容量保持率达到95.3%,倍率放电能力较好,有机蒙脱石的加入可改善电池的电极界面性质,提高电池充放电循环性能。     

PEO/LiClO_4-(PC)_x-(SiO_2)_y电解质薄膜的制备及性能

以聚环氧乙烷(PEO)/高氯酸锂(LiClO_4)为基体材料,碳酸丙烯酯(PC)为增塑剂,正硅酸乙酯(TEOS)水解制得的纳米SiO_2为掺杂相,采用匀胶法制备了PEO/LiClO_4-(PC)_x-(SiO_2)_y电解质薄膜,考察了PC单掺和PC-SiO_2共掺对电解质薄膜微观形貌、电性能和物相结构的影响。结果表明,随着PC掺量的增加,室温下电解质薄膜离子电导率呈现先增加后减小的趋势,PEO/LiClO_4-(PC)0.4电解质薄膜的电导率达到极值6.26×10~(-6)S/cm,与未增塑PEO/LiClO_4薄膜相比提高了66%,表面平整度有所提高但仍存在少量波纹。PC与纳米SiO2共掺时制备的PEO/LiClO_4-(PC)0.4-(SiO_2)0.08电解质薄膜离子电导率达到最高值为1.55×10-5 S/cm,与PEO/LiClO_4-(PC)0.4电解质薄膜极值相比提高了1.5倍,薄膜表面平整。X射线衍射分析表明,PC和纳米SiO_2的加入大大降低了PEO的结晶度,有利于提高电解质薄膜的离子电导率。