多级异质结构纳米材料的可控合成及其电化学性能

发布时间：2018-04-23 22:37

本文选题：纳米材料 + 金属基纳米复合材料　；参考：《安徽师范大学》2015年硕士论文

【摘要】：随着科学技术的快速发展以及电子产品的更新换代、能源需求的增加引起了人们普遍关注,加之近几年来环境污染的日益严重,大大加速了人们对高效的、清洁的、无污染的新型能源材料的研究。纳米材料作为新兴无机材料,由于其在电学、热学、力学、光学、磁学等方面表现出了一些传统材料所不具备的优势,特别是在催化、能量存储(超级电容器、锂离子电池)等新型能源材料方面表现出了自己独特的优势。本文主要采用简单的溶剂热合成技术,以金属锌、镍等为基底,在其上面成功实现了超薄氧化锌纳米薄膜(ZnO Nanofilm)、三维鞭炮状氧化锌异质结构纳米材料(3D ZnO Nanoarchitecture)、ZnCo2O4@MnO2纳米管阵列、CoNi2S4纳米线阵列、ZnO@MnO2@PPy三元核壳纳米棒阵列复合材料的可控合成。同时,此类生长在金属基底上的纳米复合材料,可直接用做电极材料,制备超级电容器,研究发现,该类电极展现出良好的电化学性能。具体内容如下:1、在金属锌基底上,通过简单的水热法,在没有加入任何表面活性剂的前提下,成功实现了超薄氧化锌纳米薄膜的可控合成。生长在金属锌基底上的纳米材料,可直接作为工作电极,检测溶液中的葡萄糖和水合肼。研究结果表明,该复合电极在葡萄糖的氧化和水合肼的还原方面表现出了优越的催化性能。如:该复合电极在检测葡萄糖时,具有宽的检测范围(1 uM-19.2 mM)和低的检测限(1 uM(S/N=3))。此外,对水合肼的检测也展示出宽的检测范围0.5 uM-14.2mM和低的检测限0.5 uM(S/N=3)。更重要的是,该复合电极展示了高的灵敏性、好的稳定性、好的生物兼容性。2、在金属锌基底上,利用简单的水热法,成功合成了三维鞭炮状氧化锌异质结构纳米材料。在锌基底上直接合成的三维鞭炮状氧化锌异质结构纳米材料直接被作为复合电极,用于检测水合肼和作为水合肼燃料电池的催化剂。其结果展示,三维鞭炮状氧化锌异质结构纳米材料具有较高的催化性能。同时,所制备的样品还展示出较高的紫外光吸收性能,可大大的增强光催化降解甲基橙的催化活性。因此,这种三维鞭炮状氧化锌异质结构纳米材料在燃料电池和光催化降解甲基橙方面有着潜在的应用价值。3、在泡沫镍基底上,成功设计和合成了ZnCo2O4@MnO2纳米管核壳电极。作为赝电容电极材料,Zn Co2O4@MnO2核壳纳米管电极展示出了高的具体电容,在电流密度为5 A g-1(6 mA cm-2)时,具体电容达到了1981 F g-1(2.38 F cm-2),同时,展示出了非常好的循环稳定性。此外,一款基于ZnCo2O4@Mn O2纳米管核壳电极作为正极,α-Fe2O3作为负极的、价格低廉、高性能的非对称超级电容器被成功设计。该非对称超级电容器的电压范围达到了1.3 V,在电流密度为2.5 mA cm-2时,实现了高的具体电容161 F g-1和大的能量密度37.8Wh Kg-1。4、在泡沫镍基底上,通过阴离子交换,线状CoNi2S4纳米材料被可控合成。实验结果表明,这种线状CoNi2S4纳米材料电极显示出了较高的具体电容,在电流密度为5 mA cm-2时,达到了2424 F g-1,对应的面积电容为4.85 F cm-2。此外,在电流密度为5 mA cm-2时,进行充放电循环5000次,电容量仍然保持在原来电容的86%,表明该电极材料具有良好的循环稳定性。5、在金属锌基底上,通过层-层反应,成功合成了ZnO@MnO2@PPy三元核壳纳米棒阵列(NRAs)。在这个过程中,电沉积吡咯单体在ZnO@MnO2核壳结构纳米材料的表面上,优化了电荷传递进程的同时,提高了该材料的电化学性能。由于电荷传递能力的增强,ZnO@MnO2@PPy三元核壳纳米棒阵列电荷转移电阻被降低,电化学性能得到改善。研究结果显示,这个三元核壳纳米棒电极能够提供较高的具体电容(电流密度为2.5 A g-1时具体电容为1281 F g-1)和面积电容(电流密度为3.5 mA cm-2时面积电容为1.793 F cm-2)。此外,此电极在电流密度为5 A g-1时进行5000次充放电循环后,电容量仍保持为原来的90%,表明ZnO@MnO2@PPy三元核壳纳米棒电极具有优异的循环稳定性。
[Abstract]:With the rapid development of science and technology and the renewal of electronic products, the increase of energy demand has aroused widespread concern. In addition, environmental pollution has become more and more serious in recent years. It has greatly accelerated the research of new energy materials which are efficient, clean and pollution-free. As a new inorganic material, nanomaterials are in electricity. Studies, heat, mechanics, optics and magnetism show some advantages that traditional materials do not possess, especially in the new energy materials such as catalysis, energy storage (supercapacitor, lithium ion battery) and other new energy materials. This paper mainly uses a simple solvent thermal synthesis technology, based on metal zinc and nickel as the base. The super thin Zinc Oxide nano film (ZnO Nanofilm), the three dimensional firecracker like Zinc Oxide heterostructure nanomaterial (3D ZnO Nanoarchitecture), the ZnCo2O4@MnO2 nanotube array, the CoNi2S4 nanowire array, the ZnO@MnO2@PPy three element core shell nanorod array composite material controlled synthesis. At the same time, this kind of growth is on the metal substrate. Nano composite materials can be used directly as electrode materials to prepare supercapacitors. It is found that the electrodes exhibit good electrochemical performance. 1, on the metal zinc substrate, the controllability of ultra-thin Zinc Oxide Nanothin films has been successfully realized by simple hydrothermal method before adding any surface active agent. Nanomaterials on the metal zinc substrate can be directly used as working electrodes to detect glucose and hydrazine hydrate in the solution. The results show that the composite electrode shows superior catalytic performance in the oxidation of glucose and reduction of hydrazine hydrate. For example, the composite electrode has a wide detection range when it is detected in glucose (1 UM-19.2 mM) and low detection limit (1 uM (S/N=3)). In addition, the detection of hydrazine also shows a wide detection range of 0.5 uM-14.2mM and a low detection limit of 0.5 uM (S/N=3). More importantly, the composite electrode exhibits high sensitivity, good stability, good biological facultative.2, and a successful combination of a simple hydrothermal method on a metal zinc base. Three dimensional firecracker like Zinc Oxide heterostructure nanomaterials are formed. The three-dimensional flagellate Zinc Oxide heterostructure nanomaterials directly synthesized on the zinc substrate are directly used as composite electrodes to detect hydrazine hydrate and hydrazine hydrate fuel cells as catalysts. The results show that the three-dimensional flagellate Zinc Oxide heterostructure nanomaterials have a better effect. At the same time, the prepared samples also exhibit high UV absorption properties, which can greatly enhance the catalytic activity of photocatalytic degradation of methyl orange. Therefore, this three-dimensional firecracker like Zinc Oxide heterostructure nano material has potential application value.3 in the fuel cell and photocatalytic degradation of methyl orange, in the foam nickel base At the end, the ZnCo2O4@MnO2 nanotube core shell electrode was successfully designed and synthesized. As a pseudo capacitance electrode material, the Zn Co2O4@MnO2 nuclear shell nanotube electrode showed a high specific capacitance. When the current density was 5 A g-1 (6 mA cm-2), the specific capacitance reached 1981 F g-1 (2.38 F cm-2). At the same time, a very good cycle stability was shown. Besides, A low price, low price, high performance asymmetric supercapacitor based on the ZnCo2O4@Mn O2 nanotube core electrode as the cathode, and the high performance asymmetric supercapacitor is successfully designed. The asymmetric supercapacitor has a voltage range of 1.3 V and a high specific capacitance of 161 F g-1 and a large energy density 37.8 at a current density of 2.5 mA cm-2. Wh Kg-1.4, on the foam nickel substrate, is controlled by anion exchange, linear CoNi2S4 nanomaterials are synthesized. The experimental results show that this linear CoNi2S4 nanomaterial electrode shows a high specific capacitance. When the current density is 5 mA cm-2, it reaches 2424 F g-1, the capacitance to the area is 4.85 F cm-2. in addition, and the current density is 5. At mA cm-2, the charge discharge cycle is carried out for 5000 times, and the capacitance remains at 86% of the original capacitance. It indicates that the electrode material has a good cyclic stability.5. On the metal zinc substrate, the ZnO@MnO2@PPy three element nuclear shell nanorod array (NRAs) is successfully synthesized by layer layer reaction. In this process, the electrodeposited pyrrole monomer is in the ZnO@MnO2 nuclear shell. On the surface of the structured nanomaterials, the electrochemical performance of the material is improved while the charge transfer process is optimized. The charge transfer resistance of the ZnO@MnO2@PPy three element nuclear shell nanorod array is reduced and the electrochemical performance is improved. The results show that the three element nuclear shell nanorod electrode can be provided. Higher specific capacitance (the specific capacitance is 1281 F g-1 when the current density is 2.5 A g-1) and area capacitance (the area capacitance is 1.793 F cm-2 when the current density is 3.5 mA cm-2). Furthermore, after the electrode has 5000 charging and discharging cycles at the current density of 5 A g-1, the capacitance remains 90%, indicating the ZnO@MnO2@PPy three yuan nuclear shell nanorods. The electrode has excellent cyclic stability.

【学位授予单位】：安徽师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.1;O646

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