磷系取代型杂多化合物电解质的制备与导电性能研究

发布时间：2018-05-25 21:23

本文选题：杂多酸 + 离子液体　；参考：《浙江大学》2017年博士论文

【摘要】：杂多酸或多金属含氧酸盐是一类重要的含有氧桥的多核配合物,具有特殊的结构和独特的物理化学性质。针对它们的性质研究与应用已涉及到许多领域,如催化、光化学、电化学、生物医学和材料科学等。新型杂多酸及杂多酸衍生物的设计合成与性能研究是多酸化学领域的前沿和热点之一。本文合成了五种多元杂多酸H_4[In(H_2O)PW11039]·11H_20(PW11In)、H5PW10V2O40·14H_2O(PW10V2)、H8P2W16V2O62·20H_2O(P2W16V2)、H6P2W16Mo2O40·29H_2O(P2W16Mo2)和 H_4[In(H_2O)PW9Mo2039]·11H_20(PW9Mo2In),确定了合成反应的适宜条件。通过一系列手段如元素分析、红外光谱(FT/IR)、紫外光谱(UV)、X-射线粉末衍射(XRD)和热重差热分析(TG-DTA)对它们的结构和热稳定性进行了表征。在此基础上,测定了这些杂多酸在室温(18 ℃C)环境下的质子电导率,并通过测定其不同温度下的质子电导率,研究了它们的质子导电机理。实验结果表明这些杂多酸在室温下电导率均达到10-4 S·cm-1以上,为新型固体高质子导体,它们的质子导电机理均为Vehicle机理。除此之外,以含磺酸基的咪唑类(MIMPS)、吡啶类(PyPS)、季胺类(TEAPS)离子液体阳离子以及三丁基十四烷基氯化擕(TBTPC1),季铵类离子液体((C4H9)3N(C10H_21)Br(TBDABr)、(C4H9)3N(C14H_29)Br(TBTABr)、(C8H17)3NCH3Cl(TOAMeCl))为原料,分别与多元杂多酸PW11In、PW10V、P2W16V2、P2W16Mo2和其它磷系多元杂多酸(H7[In(H_2O)P2W17O61](P2W17In)、H7P2W17VO62(P2W17V)、H9P2W15V3O62(P2W15V3)和 H_4PW11VO40(PW11V))化合,合成了—系列新型杂多化合物离子液体:[MIMPS]8P2W16V2O62、[MIMPS]6H_2P2W16V2O62、[MIMPS]4H_4P2W16V2O62、[MIMPS]5PW10V2O40、[MIMPS]3H_2PW10V2O40、[PyPS]8P2W16V2O62、[PyPS]5PW10V2O40、[TEAPS]5PW10V2O40、[TEAPS]7P2W17VO62、[TEAPS]8P2W16V2O62、[TEAPS]9P2W15V3O62、[TBTP]5PW10V2O40、[TBTP]8P2W16V2O62、[TOAMe]4[In(H_2O)PW11O39]、[TOAMe]7[In(H_2O)P2W17O61]、[TOAMe]4PW11VO40、[TBDA]8P2W16V2O62 和[TBTA]8P2W16V2O62。在此基础上,以特定的分类方式对它们分别加以讨论。通过IR、UV、XRD、TG-DTA和TEM等一系列分析手段对这些离子液体的结构和热稳定性进行了表征,同时也研究了它们的电化学性能。TG-DTA曲线表明所有离子液体在100℃C以下均能发生可逆相转变过程,是新型温度控制型离子液体。实验结果显示产物的阴阳离子种类与其物理化学性质之间有密切关系:酸式盐比相应的正盐在热稳定性和电导率上更高,并且随着氢离子数目的增加而增加;对于同种阳离子,比如三丁基十四烷基擕和三辛基甲基铵来说,Dawson结构多酸离子液体中比Keggin结构具有更高的电导率;但当阳离子不同时,碳链较短的阳离子(TBDA)往往比碳链较长的阳离子(TBTA)具有更高的电导率。相变过程将显著提高其电导率,高温下所有离子液体的电导率均达到10-4 S·cm-1以上,而且它们可以在100℃以下经历相变,同时电导率大幅度提高,证明它们是新型相变多酸离子液体。
[Abstract]:Heteropoly or polyoxometalates are one of the most important Polyoxometalates Containing Oxygen bridges, with special structures and unique physical and chemical properties. The study and application of their properties have been involved in many fields, such as catalysis, photochemistry, electrochemistry, biomedicine and material science. Synthesis and performance research are one of the frontiers and hot spots in the field of polyacid chemistry. This paper syntheses five kinds of Heteropoly heteropoly acids H_4[In (H_2O) PW11039] / 11H_20 (PW11In), H5PW10V2O40 14H_2O (PW10V2), H8P2W16V2O62 20H_2O (P2W16V2), H6P2W16Mo2O40. By means of a series of means such as elemental analysis, infrared spectroscopy (FT/IR), ultraviolet spectroscopy (UV), X- ray powder diffraction (XRD) and thermogravimetric analysis (TG-DTA), their structure and thermal stability were characterized. On this basis, the proton conductivity of these heteropoly acids at room temperature (18 C C) was measured and measured by them. The conduction mechanism of proton conductivities at different temperatures was studied. The experimental results showed that the conductivity of these heteropoly acids reached 10-4 S. Cm-1 at room temperature. It was a new solid high proton conductor, and their proton conduction mechanism was Vehicle mechanism. In addition, the sulfonic acid imidazole (MIMPS), pyridine (PyPS), and the quaternary system were used. Ammonium (TEAPS) ionic liquid cations and three butyl fourteen alkyl chloride (TBTPC1), quaternary ammonium ionic liquids (C4H9) 3N (C10H_21) Br (TBDABr) and 3N (C14H_29) Br (TBTABr) are used as raw materials. 17In), H7P2W17VO62 (P2W17V), H9P2W15V3O62 (P2W15V3) and H_4PW11VO40 (PW11V) combine to synthesize a series of new heteropoly compound ionic liquids: [MIMPS]8P2W16V2O62, [MIMPS]6H_2P2W16V2O62, [MIMPS]4H_4P2W16V2O62, [MIMPS]5PW10V2O40, [MIMPS]. 62, [TEAPS]8P2W16V2O62, [TEAPS]9P2W15V3O62, [TBTP]5PW10V2O40, [TBTP]8P2W16V2O62, [TOAMe]4[In (H_2O) PW11O39], [TOAMe]7[In (H_2O) P2W17O61], [TOAMe]4PW11VO40, [TBDA]8P2W16V2O62, and, on this basis, discuss them in a specific way. The structure and thermal stability of these ionic liquids were characterized, and their electrochemical performance.TG-DTA curves showed that all ionic liquids could have reversible phase transition process under 100 centigrade C. It was a new type of temperature controlled ionic liquid. The experimental results showed that the types of ions and yang ions of the products and their physical and chemical properties were found. There is a close relationship between the quality: the acid salt is higher in the thermal stability and the conductivity than the corresponding positive salt, and increases with the increase of the number of hydrogen ions; for the homologous cations, such as three butyl fourteen alkyl groups and three octyl ammonium, the conductivity of the Dawson structure polyacid ionic liquid is higher than that of the Keggin structure; but Dangyang is the same. When ions are different, the shorter cations (TBDA) tend to have higher electrical conductivity than the longer cations (TBTA). The phase transition process will significantly increase the conductivity. The conductivity of all ionic liquids at high temperatures is up to 10-4 S. Cm-1, and they can undergo phase transitions below 100 C, and the conductivity is greatly improved. It is clear that they are new phase change polyacid ionic liquids.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4

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