Studies on the room temperature conductivity of PEO-LiClO4-Al2O3 composite polymer electrolyte

A composite polymer electrolyte of Polyethylene oxide (PEO)-LiClO4 containing fine Al2O3 particles was studied by using differential scanning calorimetry, infrared spectroscopy and electrochemical impedance spectroscopy. Compared with the polymer electrolyte without Al2O3 particles, the glass transition temperature and the degree of crystallinity were decreased, and the room temperature conductivity of PEO-LiClO4-Al2O3 composite polymer electrolyte was considerably enhanced. Moreover, the equivalent circuits and the effect of dc potential on impedance spectroscopy were discussed.

Impedance study of (PEO)(10)LiClO4-Al2O3 composite polymer electrolyte with blocking electrodes

A composite solid polymer electrolyte (SPE) of (PEO)(10)LiClO4-Al2O3 was prepared and Pt and stainless steel(SS) blocking electrodes were used for an impedance study. It was found that the semicircle in the high frequency range and the straight line in the low frequency range depend upon different blocking electrodes and polarization potentials applied in the experiments. In the equivalent circuit. two constant phase elements (CPE) have been used instead of the pure geometrical and double layer capacitances. respectively. A theoretical line calculated from their estimated values has a good correlation with the experiment data. Moreover. the equivalent circuit also can be used to explain the impedance properties of Pt and stainless steel (SS) blocking electrodes both in the high and the low frequency ranges. (C) 2001 Elsevier Science Ltd. All rights reserved.

In-situ microscopic FTIR spectroelectrochemistry of ascorbic acid in poly(ethylene glycol)/LiClO4 electrolyte paste and in the presence of dispersed cobalt hexacyanoferrate microcrystalline powder

In-situ microscopic FTIR spectroelectrochemical technique(MFTIRs) was applied to studying the electrochemical oxidation of ascorbic acid(AA) in poly(ethylene glycol)(PEG) paste at a 100 mu m diameter Pt disk electrode. Using this technique, the catalytic ability of cobalt hexacyanoferrate(CoHCF) microcrystalline toward AA oxidation was also studied, it was found that the dispersed CoHCF powder in the PEG paste can generate well-shaped thin-layer cyclic voltammetric waves with the peak height proportional to the scan rate, corresponding to the Fe centered redox reactions. This oxidation step catalyzed the AA oxidation. Also, this pasted CoHCF powder generated well-resolved in-situ MFTIRs spectra, by which a chemical interaction between C = C bond of AA ring and CoHCF lattice was revealed. A corresponding surface docking mechanism for the catalytic reaction has been proposed.

In situ microscopic FTIR spectroelectrochemistry study of oxidation of L-ascorbic acid in polymer electrolyte (PEG/LiClO4)

In situ microscopic FTIR spectroelectrochemistry behavior of L-ascorbic acid (H(2)A) in polymer electrolyte is reported for the first time. H(2)A undergoes a two-step oxidation, The oxidation waves shift towards more anodic potential values when the scan rate increases. The peak currents of the oxidation waves are proportional to the square roots of scan rate up to 100 mV/s, The in situ infrared spectra suggest that the product of the oxidation be dehydroascorbic acid, which may exist as a dimer.

Thermal, mechanical and ionic conductive behaviour of gamma-radiation induced PEO/PVDF(SIN)-LiClO4 polymer electrolyte system

An effort has been made to modify the mechanical behaviour of our previously reported gel-type gamma-radiation crosslinked polyethylene oxide (PEO)-LiClO4 polymer electrolyte. A highly polar and gamma-radiation crosslinkable crystalline polymer, polyvinylidene fluoride (PVDF), was selected to blend with PEO and then subjected to gamma-irradiation in order to make an simultaneous interpenetrating network (SIN), which was used as a polymer host to impart stiffness to the plasticized system. Experimental results have shown that the presence of PVDF in the system, through gamma-radiation induced SIN formation, could not only give a rather high mechanical modulus of 10(7) Pa at ambient temperature, but also maintain the room temperature ionic conductivity at a high level (greater than 10(-4) S/cm). DSC, DMA and conductivity measurement techniques were used to examine the effects of blending, gamma-irradiation and plasticization on the variations of glass transition and melting endotherm, on the appearance of high elastic plateau and on the temperature dependence of ionic conductivity: In addition, it was found that, in contrast with the unplasticized system, the ionic conductivity mechanism of this gel-type electrolyte seems to conform to the Arrhenius model, suggesting that, as a result of the high degree of plasticization, the polymer chains act mainly as the skeleton of the networks or polymer cages to immobilize the liquid electrolyte solution, whereas the ionic species migrate as if they were in a liquid medium. (C) 1997 Elsevier Science Ltd.

GAMMA-RADIATION INDUCED CROSS-LINKED PEO-LICLO4 SOLID-ELECTROLYTE SYSTEM

Aimed at raising the room temperature ionic conductivity of PEO-based solid polymer electrolyte and considered that the ionic conduction preferentially occurs in the amorphous phase, we lightly crosslinked the high MW PEO through gamma-irradiation and further suppressed the residual crystallinity by plasticizing with propylene carbonate. By incorporating LiClO4 salt to the above described polymer host, the ambient (25 degrees C) ionic conductivity of the electrolyte system could reach as high as 6.8 X 10(-4) S/cm. As the electrolyte was a crosslinked system, it was mechanically self-supportable. Based on the preliminary results of the electrochemical performance of the secondary lithium battery, assembled by using this kind of solid electrolyte and polyaniline as positive electrode, it is realized that the electrolyte thus prepared is of high expectancy.

IONIC-CONDUCTIVITY AND DYNAMIC MECHANICAL RELAXATION OF A 2-COMPONENT EPOXY NETWORK-LICLO4 ELECTROLYTE SYSTEM

The correlation between mechanical relaxation and ionic conductivity was investigated in a two-component epoxy network-LiClO4 electrolyte system. The network was composed of diglycidyl ether of polyethylene glycol (DGEPEG) and triglycidyl ether of glycerol (TGEG). The effects of salt concentration, molecular weight of PEG in DGEPEG and the proportion of DGEPEG (1000) in DGEPEG/TGEG ratio on the ionic conductivity and the mechanical relaxation of the system were studied. It was found that, among the three influential factors, the former reinforces the network chains, reduces the free volume fraction and thus increases the relaxation time of the segmental motion, which in turn lowers the ionic conductivity of the specimen. Conversely, the latter two increase the free volume and thus the chain flexibility, showing an opposite effect. From the iso-free-volume plot of the shift factor log at and reduced ionic conductivity, it is noted that the plot can be used to examine the temperature dependence of segmental mobility and seems to be useful to judge whether the incorporated salt has been dissociated completely. Besides, the ionic conductivity and relaxation time at constant reference temperature are linearly correlated with each other in all the three cases. This result gives an additional experimental confirmation of the coordinated motion model of the ionic hopping with the moving polymer chain segment, which is generally used to explain the ionic conduction in non-glassy amorphous polymer electrolytes.

2-COMPONENT EPOXY NETWORK-LICLO4 POLYMER ELECTROLYTE

An epoxy network-LiClO4 electrolyte system was prepared from diglycidyl ether of polyethylene glycol and triglycidyl ether of glycerol, cured in the presence of LiClO4 only. Various techniques were used to characterize the chemical structure of the precursors and the correlation between the viscoelasticity and conductivity of the cured films was examined.

有机近红外电致变色器件

光通讯近年来发展迅速，正在从元件向集成发展，迫切需要利于集成的元件。主要的一些光学元件如激光器、放大器等均采用无机材料，连接和集成存在困难。发展易于集成的有机光学元件是目前该领域研发的一个热点。电致变色是一个古老的题目，一般都在可见区，而光通讯波长主要是1300和1550nm，是近红外区。在近红外区的工作刚刚开始，．用于光衰减器的研究已有报道，但还没有达到实际要求，寻找新型的电致变色材料及其适合这些材料的新的器件构型是目前研究的重点。本文研究了三种新的有机近红外电致变色材料及其器件：PEDOT:PSS、Ru星状化合物和酞警噜。本文通过电化学、吸收光谱、X射线衍射、AFM等实验方法和手段表征了样品的本体性质、近红外电致变色，性质和器件性能。结果如下：本论文首先研究了PEDOT:PSS的近红外电致变色性质。实验结果首次表明通过掺杂如Liclo4的电解质可以提高近红外电致变色器件的性能。通过掺杂，褪色时间从30秒缩短到2.8秒，着色时间从9.2秒缩短到2.7秒，变色效率从105cm2／C提高到3llcm2／C。掺杂后薄膜离子导电率提高是器件性能改善的原因。另外还制备了基于不同厚度的PEDOT：PSS薄膜的器件，发现对于一定掺杂浓度有一个最佳的厚度，在这个厚度下器件有较大的调制能力和较小的透过损失。本论文第二部分研究Ru星状化合物。通过对基于Ru星状化合物溶液的动力学的研究，证明了调制能力与溶液浓度和外加电压的关系。之后研究开发了有新构型的近红外电致变色器件，以Ru（II，II）态化合物溶液代替其交联薄膜和电解质层来形成固液型器件，同时改善了氧化钨的制备方法。将器件对1550nm光的调制能力从文献报道的2dB提高到16dB。本论文还首次报道了酞警噜的近红外电致变色性质，发现它既可以作为阳极电致变色材料也可以作为阴极电致变色材料。酞普噜的溶液和薄膜均可用于制备电致变色器件，器件的响应速度分别为23秒和1秒。但因为中性态酞警噜对1300nm和1550nm的光吸收较小，器件的调制能力也较小（-0.3dB）。 论文的最后部分详细阐述了有机光电器件表征系统的搭建及测量方法，包括电调制光的电致变色器件测试系统、光转换为电的有机光电二极管或太阳能电池等光电器件测试系统和电转换为光的有机电致发光二极管的器件测试系统。本论文的结果证明采用新构型可以提高近红外电致变色器件的性能；通过掺杂可以缩短电致变色器件的响应时间和提高其变色效率；同时还首次报道了酞瞥噜的近红外电致变色性质。

Electrochemical study of PW12O403- in poly(ethylene glycol) electrolyte

The electrochemical properties Of PW12O403- (abbreviated as PW12) anion in poly(ethylene glycol) (PEG) have been studied by cyclic voltammetry, complex impedance and FT-IR spectroscopy. The PW12 anion in PEG-LiClO4 electrolyte shows reasonable facile electrochemistry, and the diffusion coefficients Of PW12 were measured with microelectrode. It is shown that ionic conductivity of polymer electrolytes based on low molecular weight PEG can be improved by the addition of PW12. The increase of conductivity is coupled with decrease of transient cross-links density of polymer chains which is evidenced by the downshift of C-O-C stretching mode. The phenomena are explained in view of ion-ion and ion-polymer interactions.

Electrochemical behavior of alpha-Keggin-type nanoparticles, Co(en)(3)(PMo12O40), in polyethylene glycol

The electrochemical behavior of alpha-Keggin-type nanoparticles, Co(en)(3)(PMo12O40) (abbreviated as PMo12-Co), have been studied in poly(ethylene glycol) for four different molecular weights (PEG, average MW 400, 600, 1000, and 2000 g mol(-1)) and containing LiClO4 (O/Li=100/1) supporting electrolyte. The diffusion coefficients of the PMo12-Co nanoparticles were determined using a microelectrode by chronoamperometry for PEG of different molecular weights that were used to describe the diffusion behavior of PMo12-Co nanoparticles in different phase states. Moreover, the conductivity of the composite system increases upon addition of PMo12-Co nanoparticles, which was measured by an a.c. impedance technique. FT-IR spectra and DSC were used to follow the interactions of PEG-LiClO4-PMo12-Co, and well described the reason that the PMo12-Co nanoparticles could promote the conductivity of the PEG-LiClO4-PMo12-Co system.

Study of the ionic conductivity of polymer electrolyte using imaginary impedance spectroscopy

Polymeric electrolytes of (PEO1)(10) LiClO4-Al2O3 (PEO: poly (ethyleneoxide)) and (PEO2)(16)LiClO4-EC (EC: ethylene carbonate) were prepared. We proposed an equivalent circuit and gave the meaning of the concerned circuit elements. When the impedance spectrum deformed severely, the ionic conductivity of polymer electrolyte was determined by using the maximum of imaginary impedance, which is a convenient method.

Conductive behavior and ionic conductivity of composite polymer electrolytes

The ac impedance plots of ( PEO)(16) LiClO4-EC composite polymer electrolytes were studied. The equivalent circuit of stainless steel electrode(SS)/composite electrolyte/SS system was applied to explain the ac impedance plots, The results showed that the equivalent circuit could fit the experimental data very well. The ionic conductivity was calculated using the bulk resistance that was obtained from equivalent circuit. The effect of EC on the conductive behavior was explained by the interactions among different species formed in the composite polymer electrolytes. For lower EC concentration samples, the temperature dependence of conductivity in low temperature range followed Arrhenius type, but when EC concentration was larger than 20%, the temperature dependence of conductivity obeyed the Vogel-Tamman-Fulcher (VTF) equation in all temperature ranges.

阻抗虚部计算聚合物电解质电导率

用交流阻抗法研究了 (PEO1 ) 1 0 LiClO4 Al2 O3和 (PEO2 ) 1 6 LiClO4 碳酸乙烯酯 (EC)两种复合聚合物电解质体系的电导率 ,给出了等效电路和各拟合元件的物理意义。当阻抗谱图发生严重变形时 ,提出一种比较简单的计算聚合物电解质电导率的方法———阻抗虚部最大值法

聚环氧乙烷复合聚合物电解质/惰性电极交流阻抗谱的研究

制备了PEO LiClO4 Al2 O3及PEO LiClO4 碳酸乙烯酯 (EC)两种聚环氧乙烷(PEO)复合聚合物电解质 (SPE)薄膜 ,用不锈钢及铂两种惰性电极研究了聚合物电解质的交流阻抗特性 ,并对SPE/惰性电极的界面特性进行了研究 .提出了一种具有普适性的等效电路 ,发现电导率的测定与采用的惰性电极有关 .而且交流阻抗谱图与所加交流扰动幅度无关 ,但与直流极化电势有关 .EC含量的增加对低频直线的斜率也有影响.