The nature of the interaction between polyaniline and 2,5-dimercapto-1,3,4-thiadiazole in electrochemical redox processes

The interaction between polyaniline (PAn) and 2,5-dimercapto-1,3,4-thiadiazole (DMcT) was investigated by means of cyclic voltammetry and UV-visible spectroscopy. The results show that the polymerization-depolymerization reaction of DMcT or its dilithium salt Li(2)DMcT is a kinetically quasi-reversible process. PAn exhibits very weak electrochemical activity in neutral propylene carbonate. After doping with protonic acid, such as hydrochloric acid or maleic acid etc., however, it shows an extensively enhanced electroactivity. For the complex system, PAn-DMcT or PAn-Li(2)DMcT, polyaniline has no catalytic activity for the electrochemical polymerization-depolymerization reaction of DMcT or DMcT(2-). Instead, the enhancement of the electrochemical redox activity of PAn-DMcT system compared with that of PAn, DMcT, Li(2)DMcT, and PAn-Li(2)DMcT comes from the protonic doping of PAn by DMcT.

Plasticizer effect on the ionic conductivity of PEO-based polymer electrolyte

The effects of plasticizer ethylene carbonate (EC) on the AC impedance spectra and the ionic conductivity are reported. With increasing of EC concentration the semicircle in high frequency disappears, and the slope of the straight line in low frequency decreases. The data obtained from impedance experiments can be explained using an equivalent circuit proposed. On the other hand, the room temperature conductivity increases with EC concentration because of the increase of the segmental flexibility of PEO. For lower EC concentration samples, the temperature dependence of conductivity in low temperature range follows Arrhenius type, but when EC concentration is larger than 20%, the temperature dependence of conductivity obeys the Vogel-Tamman-Fulcher (VTF) equation in all temperature ranges.

Methods to study the ionic conductivity of polymeric electrolytes using a.c. impedance spectroscopy

Composite polymeric electrolytes of PEO-LiClO4-Al2O3 and PEO-LiClO4-EC were prepared and the ionic conductivity by a.c. impedance was calculated using four different methods, and three kinds of representations of a.c. impedance spectra were adopted. The first is based on the Nyquist impedance plot of the imaginary part (Z") versus the real part (Z') of the complex impedance. The second and the third correspond to the plots of imaginary impedance Z" as a function of frequency (f), and the absolute value (\Z\) and phase angle (theta) as a function of f, respectively. It was found that the values of the ionic conductivity calculated using the three representations of a.c. impedance spectra are basically identical.

The electrochemical reversibility of the polyaniline/organodisulfide composite cathode containing an organomonothiol

Organomonothiols were used to control the extent of 2,5-dimercapto-1,3,4-thiadiazole polymerization. When organomonothiols were incorporated into polyaniline/2,5-dimercapto-1,3, 4-thiadiazole composite cathode materials for lithium batteries, their electrochemical reversibility and charge-discharge capacities were improved significantly. (C) 1999 The Electrochemical Society. S0013-4651(99)01-078-2. All rights reserved.

Enhanced redox processes of disulfides with partially N-methylated polyaniline

Partially N-methylated polyaniline (NMPAn) is used instead of polyaniline (PAn) to make a composite with organodisulfides for cathodes of lithium secondary batteries. NMPAn displays a better electrocatalytic effect on the redox processes of organodisulfides than PAn. (C) 1998 Elsevier Science S.A. All rights reserved.

An electrochemical study of prussian blue microcrystallines mixed in PEO400 polymer electrolyte by solid-state voltammetry

The electrochemistry of Prussian blue mixed in a polymer medium containing MClO4 (M = Li+, Na+, K+, TBA(+)) as the supporting electrolyte was studied by means of solid-state voltammetry. This approach is new in Prussian blue studies. The behavior of PB in polymer electrolytes is somewhat similar to the well-known behavior for an electrochemically synthesized PB film in aqueous media. Besides, K+, Li+ and Na+ ions can also transport through the crystal of PB because of its zeolitic nature. The transport of TBA(+) ions is possible. Kinetic control lies in the diffusion of cations in and out of the lattice of Prussian blue. Reduction waves of Prussian blue depend on both the size and type of cations. PB is very stable upon electrochemical cycling in polymer electrolytes and air. This system may be used in rechargeable batteries and electrochromic devices.

A new solid-state electrolyte: Rubbery 'polymer-in-salt' containing LiN(CF3SO2)(2)

A new class of rubbery 'polymer-in-salt' electrolytes for application in solid-state lithium batteries has been explored by differential scanning calorimetry and a.c. impedance analysis. Simple phase diagrams of LiN(CF3SO2)(2)+LiClO4 and LiC(CF3SO2)(3)+LiN(CF3SO2)(2) have been drawn, which are very important to determine polymer-in-salt electrolyte materials. The conductivities obtained by a.c. impedance measurement are smaller for the electrolyte that contains acetate LiOAc salt than for the electrolyte without this salt.

An investigation on ion solvation and ion association in a gel-type solid state polymer electrolyte

Ion salvation and ion association in polytriethylene glycol dimethacrylate (PTREGD)-LiClO4 gel-type polymer electrolytes were investigated. It was found that the fraction of solute existing as single ions (alpha(i)) decreases and that of triple ions (alpha(i)) increases linearly with increasing LiClO4 concentration, while for ion pairs, as the salt concentration increases, its fraction (alpha(p)) increases first and then falls down. The findings can be rationalized by the fact that the ionic conductance of the polymer electrolyte may be mainly contributed by triple ions and higher ionic aggregates with unequal numbers of positive and negative charges in the salt concentration range of practical significance, i.e. in the range of 0.5-1.5 mol/l. The temperature dependence of these fractions was also examined. In the case of tetraethylene glycol as the solvent, alpha(i) and alpha(p) increase as the temperature is raised, but alpha(t) decreases as the temperature increases from 25 degrees C to 85 degrees C. It seems that the increase of alpha(i) and alpha(p) results from the redissociation of triple ions at higher temperature, The same changing trend of those fractions is also observed when PEG(400) is used as the solvent.

AN ALL-SOLID-STATE LITHIUM POLYANILINE RECHARGEABLE CELL

The performance of an all-solid-state cell having a lithium negative electrode, a modified polyethylene oxide (PEO)-epoxy resin (ER) electrolyte, and a polyaniline (PAn) positive electrode has been studied using cyclic voltammetry, charge/discharge cycling, and polarization curves at various temperatures. The redox reaction of the PAn electrode at the PAn/modifed PEO-ER interface exhibits good reversibility. At 50-80-degrees-C, the Li/PEO-ER-LiClO4/PAn cell shows more than 40 charge/discharge cycles, 90% charge/discharge efficiency, and 54 W h kg-1 discharge energy density (on PAn weight basis) at 50-mu-A between 2 and 4 V. The polarization performance of the battery improves steadily with increase in temperature.

新型轮—腿—履带复合移动机构及稳定性分析

为提高反恐防暴机器人对非结构环境的适应能力,设计出了一种具有良好的机动性能和转向性能的新型轮—腿—履带复合移动机构.通过机器人机构分析与本体的稳定性分析,论证了其结构设计的可行性及好的稳定性.

反恐防暴机器人机构与控制的研究

西方国家早在20世纪60年代就开始采用防暴机器人处理爆炸物。自从9.11事件后，国际社会恐怖活动更是愈演愈烈，许多国家相继对此给予了高度重视。反恐防暴机器人可应用于核工业、军事、燃化、铁路、公安、武警等部门，代替人在危险、恶劣、有害环境中执行探查、排除或销毁爆炸物、消防、抢救人质以及与恐怖分子对抗等任务。本项目依托课题由最初的“危险作业机器人”到现在的“反恐防暴机器人的产业化研究”，由国家“863”计划资金滚动支持。就现有的反恐防暴机器人，存在速度较慢或机动灵活性不强或可靠性不高等不足，现研究出一种新型反恐防暴机器人，目的是在保证适应一定的非结构环境的前提下（适用所有的非结构环境的移动机构设计是不可取的，也是不现实的），提高机器人本体转向性能和移动速度，降低功耗，机构简单化，同时在硬件与软件设计时采取一些相应的措施，提高其在实际应用环境中的可靠性和抗干扰能力。首先，通过对以往反恐防暴机器人在非结构环境中采用的复合移动机构对比分析研究，提出了一种新型的轮-履带-腿复合移动机构，应用在”灵豹”机器人上。它的特色是移动机构继承了“灵蜥”系列反恐防暴机器人轮与履带移动方式自动切换功能，并且针对“灵蜥”系列机器人轮式移动时，四轮滑动转向灵活性不高、功耗大的问题，提出了三轮式移动机构，在狭小移动空间有着广泛的应用。并对该机器人本体做了运动学分析和稳定性分析，论证了该机构的可行性。其次，根据课题项目研究的需要，在控制方面，主要完成了“灵狐”小型反恐防暴机器人的系统构建与功能实现。通过从事“灵蜥”系列机器人项目开发，积累了一些移动机构设计与分析以及控制系统一些问题解决的实际经验，在“灵狐”控制系统设计过程中，由于采用单片机作为微控制单元，因此着重考虑了提高系统可靠性与抗干扰能力。在“灵狐”机器人样机试验中取得了好的效果，均达到预期目标。

锂离子电池组合前后的特性研究

为更好地使用锂离子电池组,更精确地估算电池的荷电状态(SOC),对锂离子电池组合前后进行了常温4.0 A充放电、常温7.5 A放电、-20℃下4.0 A放电以及55℃下4.0 A放电等实验测试。实验结果显示:锂离子电池成组后的充放电特性有所下降,电池组总容量下降为单体电池的90%左右,SOC偏低,工作电压的下降速率在放电末期急剧上升,可达平台区的50倍。对电池组的一致性进行了分析,得出锂离子电池成组时应充分考虑单体电池的一致性;在估算SOC时,采用电池组参数和单体电池参数相结合的方式。