Ionic Conduction in Polymers

Abstract

The mechanism of ionic current flow through three polymer films immersed in electrolyte was investigated using current-voltage measurements. Results suggest that conductivity changes result from changes in the dissociation energy of ionogenic groups on ingress of water.     

Ionic Conduction of ANovel Comb Polvmer Electrolyte Based on Maleic Anhydride Copolymer with Oligo－oxyethylene Side Chains

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Investigation of the Ionic Conduction Mechanism in Carboxymethyl Cellulose/Chitosan Biopolymer Blend Electrolyte Impregnated with Ammonium Nitrate

In the present work, an attempt has been made to prepare a new natural biopolymer blend electrolyte of carboxymethyl cellulose/chitosan impregnated with NH₄NO₃ by the solution casting technique. The conductivity for the system was measured by impedance spectroscopy. The incorporation of 40 wt.% NH₄NO₃ optimized the ambient temperature conductivity of the electrolyte up to 1.03 × 10^?5 S cm^?1. All electrolytes were found to follow the Arrhenius relationship. Dielectric studies confirmed that the electrolytes obey non-Debye behavior. The temperature dependence of the power law exponent s for the highest conducting film can be represented by the correlated barrier hopping model.     

Design of Single Ionic Conduction in Polymeric Solid Electrolytes

Oligo(oxyethylene) methacrylate, MEO, has been synthesized as a basic material to design a polymeric solid electrolyte. The homopolymer P(MEO) has a glass transition temperature of -78°C. P(MEO) solubilizes inorganic salts without solvent, and the dissociated ions migrate fast to give very high ionic conductivity, above 10^?5 S/cm for ac. Although the ac conductivity is high, the current decreases gradually under dc conditions. This is improved by the design of an ionic conductor using only cations. Poly[oligo(oxyethylene) methacrylate-co-alkali metal methacrylate], P(MEO-MAM), is prepared as an organic solid electrolytes which allows cationic single-ion conduction. The ionic conductivity of the films depends on the electrolyte content, the dissociation energy of the comonomeric electrolytes, and the degree of segmental motion surrounding the ions in the polymer matrix. The ionic conductivity of Li or K is around 10^?6 S/cm in these polymeric systems at 80°C. The plot of logarithmic conducticity vs reciprocal absolute temperature is a curved line. The Williams-Landel-Ferry parameters, calculated from the temperature dependence of the conductivity, coincided with theoretical values within a certain range. The single-ion conduction in these films is concluded to be affected considerably by the segmental motion of the matrix polymer. This is also confirmed by the Vogel-Tammann-Fulcher plot.     

电解质溶液的总复习

在电解质溶液单元的迎考复习中,通过有明确教学目标的讲练和一定数量的测试练习,使学生掌握有关电解质溶液知识的结构和规律,以达到灵活应用、准确表达并促进智能发展的目的。为了使学生熟练掌握重要的“知识点”,可从五方面设计和实施。     

Ionic Liquid Crystalline Calixarene with Photo-Switchable Proton Conduction

We have developed a new strategy for the preparation of a light-responsive ionic liquid crystal (LC) that shows photo-switchable proton conduction. The ionic LC consists of a bowl-shaped calix[4]arene core ionically functionalized with azobenzene moieties. The non-covalent architectures were obtained by the formation of ionic salts between the carboxylic acid group of an azo-derivative and the terminal amine groups of a calixarene core. The presence of ionic salts results in a hierarchical self-assembly process that extends to the formation of a nanostructured lamellar LC arrangement (smectic A phase). In this LC phase, the ionic LC calixarene is able to display proton conductive properties, since the ionic nanosegregated areas (formed by the ionic pairs) generate the continuous channels that favor proton transport. The optical and photo-responsive properties were studied by UV-Vis spectroscopy, demonstrating that the azobenzene moieties of the ionic LC undergo reversible (E)-to-(Z) isomerization by irradiation with UV light. Interestingly, this (E)-to-(Z) photoisomerization results in a decrease of the proton conductivity values since the bent-shaped (Z)-isomer disrupts the lamellar LC phase. This isomerization process is totally reversible and leads to an ionic LC material with unique photo-switchable proton conductive properties.     

Structural Design of Ionic Conduction Paths in Molecular Crystals for Selective and Enhanced Lithium Ion Conduction

The molecular crystals [Li{N(SO₂CF₃)₂}{C₆H₄(OCH₃)₂}₂] and [Li{N(SO₂CF₃)₂}{C₆F₂H₂(OCH₃)₂}₂] with solid‐state lithium ion conductivity have been synthesized by the addition of two equivalents of 1,2‐dimethoxybenzene or 1,2‐difluoro‐4,5‐dimethoxybenzene to Li{N(SO₂CF₃)₂}, respectively. Single‐crystal X‐ray diffraction analysis revealed the formation of ionic conduction paths with an ordered arrangement of lithium ions in these crystal structures, afforded by the self‐ assembled stacking of molecular‐based channels consisting of N(SO₂CF₃)₂ anion and 1,2‐dimethoxybenzene frameworks as a result of intermolecular aromatic and hydrogen interactions. These compounds show selective lithium ion conductivity as the anions behave as a component unit of the conduction paths. The relationship between the crystal structure and ionic conductivity of the molecular crystals provides a clue to the development of novel solid electrolytes based on molecular crystals showing fast and selective lithium ion conduction.     

Selected Imidazolium Ionic Liquids as a Terminating Electrolyte in Isotachophoresis

Results of application of selected imidazolium ionic liquids [especially EMIM (1-ethyl-3-methyl-imidazolium) cation] as a new type of terminating electrolyte (TE) in isotachophoresis (ITP) with conductometric detection are presented. In experiments seven different types of leading electrolyte (LE) with new terminating electrolyte were studied. After selection of parameters influenced on the analysis resolution, buffers were successfully used in control of qualitative and quantitative analysis (sodium, potassium, calcium, and magnesium) of different type of waters. The new ITP method was satisfying and basic validation parameters were assigned.     

一种可高温运行的离子液体电解质燃料电池

本文采用N-甲基咪唑为原料通过溴盐的中间步骤合成了1-乙基-3甲基咪唑磷酸二氢盐([Emim]H₂PO₄)离子液体。首先利用元素分析和核磁共振确定了其组成,并测量了该离子液体的粘度和电导性能,然后使用多孔的聚偏氟乙烯作为支撑制备了离子液体电解质复合膜,120 ℃时通过交流阻抗测得其电导率为2.7×10^-2 S·cm^-1。最后将该复合膜组装在单电池中测试了不同温度下的性能,常压下120 ℃时可获得0.85 mW·cm^-2的功率密度,结果表明该复合膜的质子传导可以完全不依赖水,从而能够实现高温操作。     

Influence of the Electrolyte Film Thickness on Charge Dynamics of Ionic Liquids in Ionic Electroactive Devices

Developing advanced ionic electroactive devices such as ionic actuators and supercapacitors requires the understanding of ionic diffusion and drifting processes, which depend on the distances over which the ions travel, in these systems. The charge dynamics of [C(4)mim][PF(6)] ionic liquid films and Aquivion membranes with 40 wt% [C(2)mim][TfO] were investigated over a broad film thickness (d) range. It was found that the double layer charging time τ(DL) follows the classic model τ(DL) = λ(D)d/(2D) very well, where D is the diffusion coefficient and λ(D) the Debye length. In the longer time regimes (t ? τ(DL)) where diffusion dominates, the charge dynamics become voltage dependent. For low applied voltage, the later stage charge process seems to follow the d(2) dependence. However, at high voltages (> 0.5 V) in which significant device responses occur, the charging process does not show d(2) dependence so that τ(diff) = d(2)/(4D), corresponding to the ion diffusion from the bulk region, was not observed.     

新型单离子梳状聚合物电解质的合成和性能研究

通过苯乙烯,α-烯丙基聚醚和烯丙基磺酸锂共聚反应,制得一种以聚烯烃为主链、侧挂聚醚和烷基磺酸锂的新型单离子梳状聚合物电解质膜(CPPL)。通过IR,GPC及DSC等对其结构与形态进行了表征。结果表明:CPPL的Tg值主要取决于单体原料配比,室温电导率可达9.3×10-5S·cm-1,电化学窗口大于5.0V。     

The Observation of Plasma Structures in Electrolyte Solution

The passage of the electrical current (the voltage 1–2 kV) through dielectric tubes filled with electrolyte solutions causes the formation of luminous plasma zones moving along the tube. The visual observations and camera control (24 frames/s) show the possibility of the simultaneous existence up to three luminous zones. They may be as cylinder with the length up to four diameters of the tube, disc or ring. The estimations result in the lifetime of these luminous objects ≤ 0.2 s. The discharge current oscillography demonstrates the sequences of the attenuated pulses modulated with the frequency of 50 Hz. This type of plasma-solution system demonstrates high efficiency modification of the polymer materials.     

常温下从离子液体电解液中电沉积金属钴

研究了离子液体镀液中Co、Zn的共沉积行为。ZnCl2-EMIC -CoCl2电解液的循环伏安曲线上出现了三个电流峰,对应的电极电位分别为250mV、50mV、-200mV（vs. Zn2+/Zn）。结合EDS成分分析,可断定这三个电流峰分别对应着Co的电沉积、Co电极上Zn的欠电位沉积和Co-Zn合金的电沉积。恒电位沉积表明,当控制阴极电位在100 mV（vs. Zn2+/Zn）左右时,可得到高纯度的钴镀层;若进行恒电流沉积,则当电流密度为85mA/cm2左右时能够得到高纯度的钴镀层。对Co、Zn的共沉积机理研究表明,Co的电沉积过程和Zn 在Co上的欠电位沉积过程均受扩散过程控制。     

室温离子液体电解质与锂离子电池碳负极材料的相容性

室温离子液体电解质与碳负极材料间的相容性是其应用于锂离子电池的关键问题之一.本文总结了室温离子液体电解质体系与碳负极材料相容性的研究现状和微观机制,阐述了不同种类的室温离子液体与碳负极材料相容性的规律和存在的问题以及改善方法.     

BaxCe0.8Y0.2O3-α固体电解质的氧离子导电性

Ba_xCe_0.8Y_0.2O_3-α(x=1.03，1，0.98) solid electrolyte samples show a single phase of orthorhombic perovskite of BaCeO₃. The oxide-ion conduction and transport number were detected in the temperature of 600～1000℃ by electrochemical oxygen permeation (oxygen pumping)， and compared with the results from the oxygen concentration cell. The relation between the ingredient of Ba and oxide-ion conduction was also researched. It was found that these electrolytes exhibited the mixed oxide-ionic and electronic hole conduction under the experimental temperature and oxygen gas. The oxide-ion transport numbers are 0.1～0.6， which are close to the results of the oxygen con-centration cell. They increase as the decrease of Ba content in the samples.     

A Long‐Life Lithium Ion Battery with Enhanced Electrode/Electrolyte Interface by Using an Ionic Liquid Solution

In this paper, we report an advanced long‐life lithium ion battery, employing a Pyr₁₄TFSI‐LiTFSI non‐flammable ionic liquid (IL) electrolyte, a nanostructured tin carbon (Sn‐C) nanocomposite anode, and a layered LiNi_1/3Co_1/3Mn_1/3O₂ (NMC) cathode. The IL‐based electrolyte is characterized in terms of conductivity and viscosity at various temperatures, revealing a Vogel–Tammann–Fulcher (VTF) trend. Lithium half‐cells employing the Sn‐C anode and NMC cathode in the Pyr₁₄TFSI‐LiTFSI electrolyte are investigated by galvanostatic cycling at various temperatures, demonstrating the full compatibility of the electrolyte with the selected electrode materials. The NMC and Sn‐C electrodes are combined into a cathode‐limited full cell, which is subjected to prolonged cycling at 40 °C, revealing a very stable capacity of about 140 mAh g^?1 and retention above 99 % over 400 cycles. The electrode/electrolyte interface is further characterized through a combination of electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) investigations upon cell cycling. The remarkable performances reported here definitively indicate that IL‐based lithium ion cells are suitable batteries for application in electric vehicles.     

Ba_xCe_(0.8)Y_(0.2)O_(3-α)固体电解质的氧离子导电性

固体电解质是指固体状态下具有较高电导率的离子导体,根据其传导离子所带电荷分为阳离子导体(如:Na+,Li+,H+等)和阴离子导体(如:F-,Cl-,O2-等)。固体电解质与液体电解质不同之处为:(1)是固态;(2)电荷载流子通常只有一种;(3)由于晶格能较大,通常在较高温度下离子才能迁移。具有实用价值的固体电解质的电导率一般在10-3S·cm-1以上,同时要求其离子迁移数要足够大。至今,已发现和合成了上百种固体电解质材料。在加速研制绿色化学电源、寻找高离子电导率、高化学稳定性、低成本的固体氧化物燃料电池(SOFC)固体电解质的研究中,ABO3钙钛矿型…     

锂离子电池电解质溶液的研究

本文报道了 5磺基水杨酸苯氧基硼酸锂 (LiB(SO3 )C6H3 (O) (COO)OC6H5)的合成及其在乙烯碳酸酯 (ED) /二甲基碳酸酯 (DMC)及丙烯酸酯 (PC) /二甲基亚砜 (DMSO)混合溶剂中电化学性能的研究 .