Designer Chemistry of Ionic Liquids and ion Gels

离子导电材料对于电化学能量储存和能量转换装置（例如电池、电容器、燃料电池和太阳能电池）是必不可少的。近年来，离子传导材料也被用于可应用于医疗用途、微机械和纳米技术的软致动器中。常规地，电解质溶液已被用作离子传导材料。例如，硫酸用于铅酸汽车电池，易燃有机电解质溶液用于锂离子电池，锂离子电池是手机和笔记本电脑的主要电源。因此，大多数电化学装置不是固体装置，而是包括挥发性液体的液体装置。离子液体是一种室温熔盐，由于其独特的性质，如： 关于我们 非挥发性、非易燃性、热稳定性和化学稳定性、高离子传导性和宽电位窗口。我们已经将注意力集中到离子液体和聚合物的组合作为新的聚合物电解质，并提出在这些离子液体中常见的乙烯基单体的原位自由基聚合提供了离子液体和所得网络聚合物的相容组合。完全兼容的组合是新的聚合物电解质，并命名为“离子凝胶”，这是具有离子液体特性的固体电解质。如果在离子液体中对功能性进行分子设计，将大大拓展离子液体和离子凝胶的应用范围。本项目主要研究了以下几个基本性质：1）离子液体和离子凝胶中的离子动力学2）在100℃以上稳定的无水质子导电离子液体及其离子凝胶的设计3）同时导电和导电的混合导电离子液体及其离子凝胶的设计核磁共振技术结合电化学阻抗技术。由组成离子液体的阳离子和阴离子的扩散系数，由NMR，离子电导率可由能斯特-爱因斯坦方程（λ_）计算<NMR>，而实验电导率（λ_<imp>）可由阻抗测量获得。本文提出λ_<NMR>/λ_<imp>可以作为离子液体中离子状态的一种度量。在无水质子导电离子液体的设计方面，我们首次发现由多种有机胺与双（三氟甲磺酰）亚胺简单结合而成的新型Bronsted酸碱离子液体是无水质子导体，遵循载体机制和Grotthuss机制的结合。当氧化还原对以高浓度溶解在离子液体中时，电子在离子液体中也是移动的。用微电极技术研究了离子液体中I^-/I_3^-氧化还原电对的电荷输运随浓度的增加而非线性增加。在[I^-]和[I_3^-]相当的氧化还原对高浓度下的电荷输运异常可归因于I^-+I_3^-→I_3^-+I^-的交换反应。少

Ion-conducting materials are essential for electrochemical energy-storage and energy-conversion devices, such as batteries, capacitors, fuel cells, and solar cells. Recently, the ion-conducting materials are also utilized in soft actuators that can be applicable to medical use, micro-machine, and nano-technology, Conventionally, electrolyte solutions have been used as the ion-conducting materials. For instance, Sulfuric acid is used for lead-acid car batteries, flammable organic electrolyte solutions are used for lithium-ion batteries that are main power source of cellar phones and lap-top computers. As a result, the most of the electrochemical devices are not solid devises but liquid devices that include volatile liquids. Thus, it has been a subject of many researchers to make the ion-conducting materials non-volatile, non-flammable, and solid.Ionic liquids are room temperature molten salts and of great interest as new electrolyte materials, because of their unique properties such as … More non-volatility, non-flammability, thermal and chemical stability, high ionic conductivity, and wide potential window. We have directed out attention to the combination of the ionic liquids and polymers as new polymer electrolytes and proposed that in situ radical polymerization of common vinyl monomers in these ionic liquids affords compatible combinations of the ionic liquids and the resulting network polymers. Completely compatible combinations are new polymer electrolytes and named "ion gels" that are solid electrolytes with the characteristic properties of the ionic liquids. If task-oriented properties are molecularly designed in the ionic liquids, he scope of the utility of ionic liquids and ion gels may greatly expand. In this project we have aimed at exploring the following fundamental and task-oriented properties.1)Ion dynamics in ionic liquids and ion gels2)Design of anhydrous proton-conducting ionic liquids and their ion gels that are stable at the temperatures higher than 100℃3)Design of mixed-conducting ionic liquids and their ion gels that can conduct both ions and electronsThe ion dynamics has been mainly explored by using PGSE-NMR technique combined with electrochemical impedance technique. From the diffusivity for both of the cations and anion, consisting the ionic liquids, from he NMR, the ionic conductivity can be calculated from Nernst-Einstein equation (λ_<NMR>), while he experimental conductivity (λ_<imp>) can be obtained by the impedance measurements. We newly proposed that the ratio, λ_<NMR>/λ_<imp>, could be a measure of he state-of ions in the ionic liquids. As for the design of he anhydrous proton conducting ionic liquids, we have found for he first time that novel Bronsted acid-base ionic liquids, derived from a simple combination of a wide variety of organic amines with bis(trifluoromethane sulfonyl)imide, are anhydrous proton conductors, following the combination of the vehicle and Grotthuss mechanisms. Electrons are also mobile in the ionic liquids when a redox couple is dissolved in them at a high concentration. We have revealed that charge transport of an I^-/I_3^-redox couple in an ionic liquid nonlinearly increases with increasing the concentration by using microelectrode technique. This anomaly of the charge transport at high concentrations of the redox couple with comparable [I^-] and [I_3^-] can be attributed to the exchange reaction of I^-+I_3^-→I_3^-+I^-. Less