Understanding and predicting the physical properties of ILs: (Monte Carlo augmented) Born-Fajans-Haber-Cycle approaches, a systematic temperature dependent experimental and theoretical investigation of the molecular and free volumes of solid and liquid IL

理解和预测离子液体的物理性质：（蒙特卡罗增强）Born-Fajans-Haber 循环方法，对固体和液体离子液体的分子和自由体积进行系统的温度依赖实验和理论研究

• 批准号: 29468086
• 负责人: Professor Dr. Thorsten Koslowski
• 金额: --
• 依托单位: Institut für Anorganische und Analytische Chemie
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2006
• 资助国家: 德国
• 起止时间: 2005-12-31 至 2015-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/29468086?language=en
• 关键词: Understanding; predicting; physical; properties; ILs

Ionic liquids (ILs) are currently receiving a great deal of attention due to their potential use in a wide range of applications. However, as the number of applications for these materials grows, we still know very little about the origins of their fundamental properties. Furthermore, there are currently very few quantitative methods to predict the properties of unknown salts. Trial and error methods must be used to design new ILs for particular applications, which limit the progress in this field. Thus, the ability to predict the properties of yet unknown ILs in a simple procedure, would allow ILs to fulfil their destiny as designer materials, which can be tailored to a specific application. In this context we have recently developed a simple, quantitative explanation of the relatively low melting temperatures of ILs (mp s). This model can be used to predict the mp s and dielectric constants of ILs with good accuracy using simple calculations and a minimum of experimental data. As such, this technique has the potential to be used by general chemists to help in the design of new ILs. In this proposal we describe how this model can be refined to improve the accuracy of its predictions as well as to solve problem cases for the method, e.g. by determining thermodynamic properties of ILs as well as solid-state structures of ambient temperature ionic liquids. Preliminary results suggest a simple relationship between the (thermochemical) molecular volume of an IL and the viscosity and conductivity of the salt. In the proposed project we will extend these correlations, both, on an experimental as well as theoretical basis. During our work on weakly coordinating anions we have discovered that the Li+ salts of fluorinated alkoxyaluminate anions [A1(ORF)4]- melt at relatively low temperatures. One of these salts has a melting point of 42-45 °C, which already classifies this material as an IL. ILs with Li+ as the cation (Li+-ionic liquids) are currently extremely rare, but have the potential for use as electrolytes in batteries and super capacitors and as Li+-ion catalysts for organic chemistry. During the proposed project we will develop the chemistry of Li+ salts of fluorinated alkoxyaluminate anions, and by changing the structure and functionality of the anion develop materials that are liquid at ambient temperatures. Moreover, we will investigate the structural features of the anion that lead to high Li+ mobility and availability for particular applications. We will be able to use the theoretical methods developed during the project to help in the design of Li+-ionic liquids and where necessary develop new models that are specific to this special type of IL.

离子液体（IL）目前因其在广泛应用中的潜在用途而受到广泛关注。然而，随着这些材料的应用数量不断增加，我们对其基本特性的起源仍然知之甚少。此外，目前很少有定量方法来预测未知盐的性质。必须使用试错法来为特定应用设计新的IL，这限制了该领域的进展。因此，如果能够通过简单的程序预测未知的离子液体的特性，将使离子液体能够实现其作为设计材料的使命，并且可以根据特定的应用进行定制。在此背景下，我们最近对离子液体 (mp s) 相对较低的熔化温度进行了简单、定量的解释。该模型可用于使用简单的计算和最少的实验数据以良好的精度预测 IL 的 mp s 和介电常数。因此，该技术有可能被普通化学家用来帮助设计新的离子液体。在本提案中，我们描述了如何改进该模型以提高其预测的准确性以及解决该方法的问题案例，例如通过确定离子液体的热力学性质以及环境温度离子液体的固态结构。初步结果表明，IL 的（热化学）分子体积与盐的粘度和电导率之间存在简单的关系。在拟议的项目中，我们将在实验和理论基础上扩展这些相关性。在我们对弱配位阴离子的研究过程中，我们发现氟化烷氧基铝酸阴离子[A1(ORF)4]-的Li+盐在相对较低的温度下熔化。其中一种盐的熔点为 42-45 °C，已将该材料归类为 IL。以Li+为阳离子的离子液体（Li+离子液体）目前极为罕见，但具有用作电池和超级电容器中的电解质以及有机化学中的Li+离子催化剂的潜力。在拟议的项目中，我们将开发氟化烷氧基铝酸阴离子的Li+盐的化学性质，并通过改变阴离子的结构和功能来开发在环境温度下呈液态的材料。此外，我们将研究导致高 Li+ 迁移率和特定应用可用性的阴离子的结构特征。我们将能够使用项目期间开发的理论方法来帮助设计锂离子液体，并在必要时开发针对这种特殊类型离子液体的新模型。