聚联苯胺纳米颗粒的制备及其电容特性研究

发布时间：2018-06-09 14:31

本文选题：导电聚合物 + 嵌段共聚物　；参考：《新疆师范大学》2017年硕士论文

【摘要】：导电聚合物具备较长的共轭链结构,独特的物理化学性能,能够在信息存储、传感器、电化学超级电容器等方面有广泛的运用。纳米结构的导电聚合物材料由于具有特殊的纳米尺寸的效应,其能够显著提高导电高分子聚合物材料的各种物理化学性质,丰富导电高分子聚合物材料的器件的功能。在导电高分子聚合物纳米结构材料的制备的诸多方法中,以嵌段共聚物为模板制备导电高分子聚合物纳米材料一直是许多研究学者的不断探索的热点。本文的主要研究内容如下:(1)通过原子转移自由基聚合法(简称为ATRP法)合成聚乙二醇嵌段-聚苯乙烯嵌段组成的两嵌段共聚物PEO113-b-PSx(x=50,58,100),以PS嵌段长度不同的共聚物PEO113-b-PSx(x=50,58,100)为模板制备聚联苯胺。通过嵌段共聚物模板合成的导电聚联苯胺具有亚微米级到纳米级棒状分布,尺寸及分布较均匀,模板的去除未破坏聚联苯胺的形貌且使其尺寸略有减小。通过调节单体用量可以得到形貌和尺寸可控的聚联苯胺。循环寿命测试显示,去模板的聚联苯胺经过500次恒流充放电循环测试之后,比电容量衰减率在10%以内。(2)通过ATRP法合成了聚乙二醇嵌段和4-乙烯基吡啶嵌段组成的两嵌段共聚物PEO-b-P4VP,以两嵌段共聚物PEO-b-P4VP为模板制备聚联苯胺部分进入纳米级,调节模板剂胶束溶液p H值,制备形貌和尺寸均可控的聚联苯胺。合成的聚联苯胺为平均直径小于200nm棒状颗粒,其直径随着模板剂胶束溶液p H的降低而增加。在电流密度为1A·g~(-1)时,聚联苯胺的比电容量为306.3 F·g~(-1),经过长时间的充放电测试,不同条件下合成的聚联苯胺的容量衰减率均很小,表现良好的循环稳定性且各样品电化学性能呈现随着直径的减小增强的趋势。(3)通过ATRP法聚合了聚乙二醇嵌段-聚丙烯酸叔丁酯嵌段组成的(PEO-b-Pt BA),并且将PEO-b-Pt BA通过三氟乙酸水解得到聚乙二醇-聚丙烯酸(PEO-b-PAA)。以两嵌段共聚物PEO-b-Pt BA及PEO-b-PAA为模板制备了亚微米至纳米级棒状聚联苯胺(PBz)颗粒。嵌段共聚物为模板合成的PBz呈现棒状分布,颗粒直径均小于200 nm且部分颗粒直径进入100 nm以内。PBz颗粒形貌均匀,尺寸均一,使用有机溶剂溶解嵌段共聚物模板未对PBz颗粒形貌未产生影响。经电化学性能测试发现不同模板合成的PBz均具有一定的电化学活性,以PEO-b-PAA为模板得到的各样品电化学性能优于PEO-b-Pt BA为模板的情况。当电流密度在1A·g~(-1)时,材料比电容量最高达到了263 F·g~(-1)。
[Abstract]:Conducting polymers have long conjugated chain structures, unique physical and chemical properties, and can be widely used in information storage, sensors, electrochemical supercapacitors and so on. Conducting polymer materials with nanostructures can significantly improve the various kinds of conductive polymer materials because of the special nano size effect. In the preparation of conductive polymer nanomaterials, the preparation of conductive polymer nanomaterials with block copolymer as template has been a hot spot for many researchers. The main contents of this paper are as follows. (1) (1) the two block copolymer PEO113-b-PSx (x=50,58100) composed of PEG Block polystyrene block was synthesized by atomic transfer radical polymerization (ATRP method), and polydiphenamine was prepared by the template of PS block copolymer PEO113-b-PSx (x=50,58100). The conductive polyaniline was synthesized by the block copolymer template. The morphology and size of polyaniline can be obtained by adjusting the amount of monomers. The cyclic life test of the template has been measured by 500 constant current charge discharge cycles. After the test, the attenuation rate of the specific capacitance is within 10%. (2) the two block copolymer PEO-b-P4VP composed of polyethylene glycol block and 4- vinyl pyridine block is synthesized by ATRP method. The polyaniline part is prepared by two block copolymer PEO-b-P4VP as a template, and the P H value of the template agent solution is adjusted. The morphology and size of the preparation are all controllable. Polyaniline. The synthesis of polyaniline is an average diameter less than 200nm rod like particles, and its diameter increases with the decrease of P H in the template solution. When the current density is 1A. G~ (-1), the specific capacity of polyaniline is 306.3 F. G~ (-1). After a long time charge and discharge test, the capacity attenuation rate of polyaniline synthesized under different conditions It was very small, showed good cyclic stability and the electrochemical properties of each sample increased with the decrease of diameter. (3) ATRP method was used to polymerized polyethylene glycol block tert butyl ester block (PEO-b-Pt BA), and PEO-b-Pt BA was hydrolyzed by three FLUOROACETIC acid to get polyethylene glycol polyacrylic acid (PEO-b-PAA). Two The block copolymers PEO-b-Pt BA and PEO-b-PAA were prepared for the preparation of sub micron to nanometer rod like polyaniline (PBz) particles. The PBz of the block copolymer was rod like distribution, the diameter of the particles was less than 200 nm and the diameter of some particles was within 100 nm and the.PBz particles were homogeneous. The size was uniform and the block was dissolved in organic solvents. The polymer template did not affect the morphology of PBz particles. The electrochemical performance test showed that the PBz with different templates had certain electrochemical activity. The electrochemical performance of the samples obtained from PEO-b-PAA was better than that of PEO-b-Pt BA as a template. When the current density was 1A g~ (-1), the maximum material capacity reached 263 F. G~ (-1).
【学位授予单位】：新疆师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O633.21

【参考文献】