Designer Chemistry of Ionic Liquids and ion Gels

离子液体和离子凝胶的设计化学

• 批准号: 14350452
• 负责人: WATANABE Masayoshi
• 金额: $ 9.79万
• 依托单位: Yokohama National University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14350452/
• 关键词: ionic liquid; ion gel; PGSE-NMR; protin conductor; Grotthuss mechanism; fuel cell; electron transport; dye-sensitized solar cell; 磁場匂配NMR; プロトン伝導; イオンダイナミックス; マイクロ電極

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

离子传导材料对于电化学能量存储和能量转换设备，例如电池，电容器，燃料电池和太阳能电池至关重要。最近，离子传导材料也用于软致动器中，可用于医用使用，微动机和纳米技术，从传统上讲，电解质溶液已用作离子传导材料。例如，硫酸用于铅酸汽车电池，可燃烧的有机电解质溶液用于锂离子电池，这是地窖手机和膝上型计算机的主要电源。结果，大多数电化学设备不是固体设计，而是包括挥发性液体的液体设备。这是许多研究人员的主题，使离子传导材料非挥发性，非易变和实心液体是室温熔融盐，并且具有新的电解质材料，因为它们具有……更不易volations，更不易vlationility，不易加力，不易用性，不易用性，热和化学稳定性，高离子稳定性，高离子的电导率，并且潜在的潜在范围。我们已经将注意力集中在离子液体和聚合物的组合中作为新的聚合物电解质，并提出，这些离子液体中普通乙烯基单体的原位根治性聚合提供了离子液体的兼容组合，并提供了所得网络聚合物的组合。完全兼容的组合是新的聚合物电解质，称为“离子凝胶”，它们是具有离子液体特性的固体电解质。如果在离子液体中设计了面向任务的特性，则在离子液体和离子凝胶效用的范围中可能会大大扩展。 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通过使用PGSE-NMR技术与电化学阻抗技术相结合探索。从由离子液体组成的阳离子和阴离子的扩散率从NMR组成，可以从Nernst-Einstein方程（λ_<nmr>）中计算离子电导率，而他的实验电导率（λ_<imp>）可以通过阻碍测量测量值获得。我们新提出的是，λ_<nmr>/λ_<imp>的比率可能是对离子液体中离子的测量值。至于他的无水质子导致离子液体的设计，我们第一次发现新型的布朗斯特酸基离子液体源自多种有机胺与BIS（三氟甲烷亚磺酮）的简单组合，是沿着汽车和GROTTHUSS的组合结合的，是无水的蛋白质导体。当将氧化还原夫妇溶解在高浓度中时，电子也在离子液体中流动。我们已经透露，在离子液体中，i^ - /i_3^ - 雷克斯夫妇的电荷转运随着使用微电极技术的增加而非线性增加，随着浓度的增加而增加。电荷传输在高浓度的氧化还原夫妇中的异常，并具有可比的[i^ - ]和[i_3^ - ]可以归因于I^ - +i_3^ - →i_3^^ - +i^ - 的i^ - +i_3^ - →I^ - 的交换反应。较少的

项目成果

H.Tokuda: "Synthesis, Characterization, and Ion-conductive Behavior in an Organic Solvent and in an Polyether of a Novel Lithium Salt of a Perfluorinated Polyimide Anion"Macromolecules. 35. 1403-1411 (2002)

H.Tokuda：“全氟聚酰亚胺阴离子的新型锂盐的合成、表征以及在有机溶剂和聚醚中的离子传导行为”大分子。

Md.A, B.H.Susan: "Bronsted Acid-Base Ionic Liquids and Their Use as New Materials for Anhydrous Proton Conductors"Chem.Commun.. 2003. 938-939 (2003)

Md.A、B.H.Susan：“Bronsted 酸碱离子液体及其作为无水质子导体新材料的用途”Chem.Commun.. 2003. 938-939 (2003)

S.Tabata: "Synthesis of A Lewis-Acidic Boric Acid Ester Monomer and Effect of Its Addition to Electrolyte Solutions and Polymer Gel Electrolytes on Their Ion Transport Properties"Electrochim.Acta. (in press). (2003)

S.Tabata：“路易斯酸性硼酸酯单体的合成及其添加到电解质溶液和聚合物凝胶电解质中对其离子传输性能的影响”Electrochim.Acta。

Sei-ichiro Tabata, Takuro Hirakimoto, Masahito Nishiura, Masayoshi Watanabe: "Synthesis of A Lewis-Acidic Boric Acid Ester Monomer and Effect of Its Addition to Electrolyte Solutions and Polymer Gel Electrolytes on Their Ion Transport Properties"Electroch

Sei-ichiro Tabata、Takuro Hirakimoto、Masahito Nishiura、Masayoshi Watanabe：“路易斯酸性硼酸酯单体的合成及其添加到电解质溶液和聚合物凝胶电解质对其离子传输性能的影响”Electroch

R.Kawano: "High Performance Dye-Sensitized Solar Cells using Ionic Liquids as Their Electrolytes"J.Photophys.Photobio.A, Chem.. (in press). (2004)

R.Kawano：“使用离子液体作为电解质的高性能染料敏化太阳能电池”J.Photophys.Photobio.A，Chem..（正在印刷中）。