【作者】 关新；

【导师】 张庆国；

【作者基本信息】 渤海大学 ， 无机化学， 2023， 硕士

【摘要】 随着绿色化学的出现,绿色溶剂的发展和应用已引起许多研究者的高度重视。离子液体（Ionic Liquid,IL）和低共熔溶剂（Deep eutectic solvent,DES）最近已成为许多工艺的首选绿色溶剂,它们的可设计性和独特的物理化学性质也使得它们具有巨大的应用潜力。但离子液体由于粘度较大而受到了许多的应用限制,因此,许多研究者将离子液体与有机溶剂混合来改善其粘度较大的缺点。所以,对于离子液体与有机溶剂混合后的离子液体二元混合体系的研究至关重要。由于低共熔溶剂具备电化学窗口宽、易生物降解等优势,是一种具有发展前景的非水系电解液。因此,针对以上两种绿色溶剂,本文进行了以下研究:（1）离子液体的合成及离子液体二元混合体系的物理化学性质研究。本文合成了新型醚基功能化离子液体1-甲氧基,乙基-3-甲基咪唑硫氰酸盐[MOEMIM][SCN],并用红外、核磁及元素分析表征了离子液体的结构。将[MOEMIM][SCN]分别与γ-丁内酯（GBL）和碳酸丙烯酯（PC）混合,制备了全浓度的混合体系,并测定了不同温度下混合体系的密度、粘度、电导率等热力学性质。使用Vogel-Fulcher-Tamman（VFT）方程描述了混合体系的粘度、电导率与温度之间的变化关系。根据密度和粘度值估算了混合体系的超额摩尔体积（V^E）和粘度偏差（Δη）,并使用Redlich-Kister（R-K）方程进行拟合。分别运用Casteel-Amis方程和Grunberg-Nissan方程探讨了电导率和粘度与摩尔分数之间的关系。（2）低共熔溶剂的物理化学性质及电化学研究。以1-乙基-3-甲基咪唑三氟甲磺酸盐[EMIM][CF₃SO₃]为氢键受体,乙二醇（EG）为氢键供体合成了低共熔溶剂,并测定了低共熔溶剂在不同温度下的热力学性质。¹H NMR证明了低共熔溶剂的结构转变。使用VFT方程和Arrhenius方程描述了低共熔溶剂的电导率与温度之间的变化关系。根据密度值估算了体系的超额摩尔体积（V^E）。并将不同比例的低共熔溶剂作为电解液,将其组装成超级电容器,进行循环伏安、交流阻抗、恒流充放电等电化学测试,发现其有作为高性能超级电容器电解液的潜力。（3）离子液体混合体系与低共熔溶剂相互作用研究。为了更好的探究混合体系内部微观作用的变化及与热力学性质之间的关系,结合基于DFT计算的COSMO-RS模型,对离子液体混合体系和低共熔溶剂体系的作用能、氢键作用以及COSMO电荷分布等微观作用进行了系统的讨论与分析,评价了混合体系的分子间相互作用情况。更多还原

【Abstract】 With the emergence of green chemistry,the discovery and application of green solvents have attracted the attention of many researchers.Ionic Liquid（IL）and deep eutectic solvent（DES）have recently become the green solvents of choice for many processes,and their designability and unique physicochemical properties make them potentially useful for many applications.However,ionic liquid is limited by many applications due to its high viscosity.Therefore,in recent years,many researchers have mixed ionic liquid with organic solvent to improve its high viscosity.Therefore,it is very important to study the binary mixing system of ionic liquid mixed with organic solvent.At the same time,low eutectic solvent is a promising non-aqueous electrolyte due to its advantages of wide electrochemical window and easy biodegradation.For the above two green solvents,the following studies were carried out in this paper:（1）The synthesis of ionic liquid and study on physical and chemical properties of ionic liquid mixture systems.In this paper,a novel ether-group functional ionic liquid（1-methoxy,ethyl-3-methylimidazole thiocyanate）[MOEMIM][SCN]was synthesized,and its structure was characterized by infrared,nuclear magnetic and elemental analysis.[MOEMIM][SCN]was mixed withγ-butyllactone（GBL）and propylene carbonate（PC）respectively,the full concentration of the mixed system was prepared,and the density,viscosity,electrical conductivity and other thermodynamic properties of the mixed system at different temperatures were determined.The relationship between viscosity,conductivity and temperature of the mixed system is described by using the Vogel-Fulcher-Tamman（VFT）equation.The excess molar volume（V^E）and excess molar viscosity（Δη）of the mixed system were estimated from the density and viscosity values,and the Redlich-Kister（R-K）equation was used for fitting.Casteel-Amis equation and Grunberg-Nissan equation were used to investigate the relationship between electrical conductivity and viscosity and molar fraction.（2）Study on physicochemical properties and electrochemistry of deep eutectic solvents.A deep eutectic solvent was synthesized with 1-ethyl-3-methylimidazol trifluoromethanesulfonate[EMIM][CO₃FO₃]as hydrogen bond acceptor and ethylene glycol（EG）as hydrogen bond donor,and its thermodynamic properties at different temperatures were measured.The VFT equation and the Arrhenius equation were used to describe the relationship between the conductivity and temperature of the low eutectic solvent.The excess molar volume（V^E）of the system is estimated based on the density value.The structure of the eutectic solvent was characterized by ¹H NMR.Using DES as electrolyte and assembling it into supercapacitors,and conducting electrochemical tests such as cyclic voltammetry,AC impedance,constant current charge and discharge,we found that it has the potential to be used as high performance supercapacitor electrolyte.（3）Study on the interaction between ionic liquid mixture systems and deep eutectic solvent.In order to better explore the change of microcosmic interaction in the mixture systems and its relationship with thermodynamic properties,combined with the COSMO-RS model based on DFT calculation,The interaction energy,hydrogen bonding and COSMO charge distribution of DES and the ionic liquid mixed system are discussed and analyzed systematically.The intermolecular interaction of the mixed system is evaluated.更多还原