炭及氧化物空心球材料的RF模板法制备及其结构与性能

发布时间：2018-04-29 11:32

本文选题：间苯二酚-甲醛 + 反相悬浮法　；参考：《哈尔滨工业大学》2010年博士论文

【摘要】： 本文以间苯二酚(R)-甲醛(F)为炭前驱体及模板,采用反相悬浮法和水热法制备了炭空心微球,氧化物空心微球,及氧化物/炭复合微球。进一步利用RF凝胶特性,结合模板技术制备了Sn-In_2O_3/炭(ITO/C)一维复合纳米材料,验证了以RF为前驱体制备空心微纳米材料的结构可控性。采用X-射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM、HRTEM)、傅立叶变换红外光谱(FT-IR)、氮气吸附等分析手段,系统研究了材料微观组织结构,分析了结构形成机理。探索了RF炭微球及ZnO/C复合微球在锂离子电池和超级电容器材料方面的应用,研究了RF炭微球结构、形态对电性能的影响。讨论了ITO/C一维复合纳米材料在气敏元件中的应用。首次以RF为炭前驱体,通过反相悬浮法,制备了形态可控的RF炭微球。实验结果表明,RF前驱体溶液的初始pH值、催化剂和表面活性剂类型是获得RF炭空心球结构,“碗状”结构和胶囊等结构的重要反应参数。分析了不同形态的RF炭微球的形成机制,研究了RF炭微球的电学性能。电化学分析结果表明,以Na_2CO_3为催化剂所制备的RF炭微球电极材料具有理想的电容行为,循环伏安性能稳定、可逆,适用于大电流下充放电。以K_2CO_3为催化剂制备的RF炭胶囊作为锂离子电池阴极材料,充放电、循环特性测试结果表明,其初始放电电容量可达1059mAh/g,且电性能稳定,循环效率可达99%,是理想的锂离子电池阴极材料。以表面功能化修饰的RF凝胶微球为模板,制备了结构完整、粒径分布均匀的氧化物空心微球。研究了不同表面修饰剂对RF凝胶微球表面改性的作用机理,分析了RF表面改性对氧化物空心微球结构的影响。通过炭化Zn~(2+)负载的RF凝胶微球,制备了ZnO/C复合微球。其稳定的循环伏安特性和法拉第氧化-还原反应效应表明,ZnO/C复合微球可作为理想的超级电容器材料。首次将ITO溶液和RF溶液组成复合前驱体,并结合多孔氧化铝(AAO)模板技术,制备了ITO/C一维复合纳米材料。讨论了ITO/RF复合前驱体中ITO浓度对ITO/C一维复合纳米结构的影响。结果表明,通过ITO与RF前驱体溶液的同步溶胶-凝胶化过程,有效地将ITO纳米颗粒复合到RF凝胶网络中形成一维纳米复合材料。气敏性测试表明,所制备的ITO/C一维复合纳米材料具有较高氢气灵敏度和较短的响应时间,可作为氢气气敏材料。以葡萄糖溶液为前驱体,利用水热法制备了结构完整、粒径分布均匀的炭微球。通过加入不同添加剂可对炭微球结构进行有效控制。以所制备的炭微球为模板,制备了多种氧化物空心微球。利用ZnCl_2/RF/葡萄糖复合体系的水热反应过程制备了结构完整的Zn/炭复合前驱体微球,通过热处理除去炭模板,并调控热处理条件,控制得到了多种形态的ZnO空心微球,为RF凝胶微球的水热制备及其在生物单糖方面的应用奠定了基础。
[Abstract]:In this paper, carbon hollow microspheres, oxide hollow microspheres and oxide / carbon composite microspheres were prepared by reversed-phase suspension method and hydrothermal method using resorcinol (R) -formaldehyde (F) as carbon precursor and template. Furthermore, the one-dimensional composite nanocomposites of Sn-In_2O_3/ ITO / C were prepared by using RF gel characteristics and template technology. The structure controllability of hollow nanocomposites prepared with RF as precursor was verified. The microstructure and formation mechanism of the materials were systematically studied by means of X ray diffraction, scanning electron microscope (SEM), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR), FT-IRT, nitrogen adsorption and so on. The microstructures of the materials were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption. The applications of RF carbon microspheres and ZnO/C composite microspheres in lithium ion batteries and supercapacitor materials were investigated. The effects of the structure and morphology of RF carbon microspheres on the electrical properties were studied. The application of ITO/C one-dimensional composite nanomaterials in gas sensor is discussed. RF carbon microspheres with controllable morphology were prepared by reverse phase suspension with RF as precursor for the first time. The experimental results show that the initial pH value of RF precursor solution, the type of catalyst and surfactant are important reaction parameters for obtaining RF carbon hollow sphere structure, "bowl" structure and capsule structure. The formation mechanism of RF carbon microspheres with different morphology was analyzed and the electrical properties of RF carbon microspheres were studied. The results of electrochemical analysis show that the RF carbon microsphere electrode prepared with Na_2CO_3 as catalyst has ideal capacitance, stable cyclic voltammetry and reversible performance. It is suitable for charging and discharging at high current. RF carbon capsules prepared with K_2CO_3 as cathode material for lithium-ion batteries were tested for charge-discharge and cyclic characteristics. The results show that the initial discharge capacity of RF carbon capsules can reach 1059mAh / g, and its electrical properties are stable. The cycle efficiency can reach 99%. It is an ideal cathode material for lithium ion battery. The surface functionalized RF gel microspheres were used as templates to prepare hollow oxide microspheres with complete structure and uniform particle size distribution. The mechanism of surface modification of RF gel microspheres with different surface modifiers was studied, and the effect of RF surface modification on the structure of oxide hollow microspheres was analyzed. ZnO/C composite microspheres were prepared by carbonized Zn~(2 loaded RF gel microspheres. The stable cyclic voltammetry and Faraday redox effect indicate that ZnO / C composite microspheres can be used as ideal supercapacitor materials. For the first time, ITO/C one-dimensional composite nanomaterials were prepared by using ITO solution and RF solution as composite precursors and combined with porous alumina (AAO) template technology. The effect of ITO concentration in ITO/RF composite precursor on ITO/C one-dimensional composite nanostructures was discussed. The results show that ITO nanoparticles are effectively recombined into RF gel network to form one-dimensional nanocomposites through the synchronous sol-gel process of ITO and RF precursor solution. The gas sensitivity test showed that the ITO/C one-dimensional composite nanomaterials had higher hydrogen sensitivity and shorter response time and could be used as hydrogen gas sensing materials. Carbon microspheres with complete structure and uniform particle size distribution were prepared by hydrothermal method using glucose solution as precursor. The structure of carbon microspheres can be effectively controlled by adding different additives. A variety of oxide hollow microspheres were prepared using carbon microspheres as template. The Zn/ carbon composite precursor microspheres with intact structure were prepared by hydrothermal reaction of ZnCl_2/RF/ glucose composite system. The carbon template was removed by heat treatment, and various forms of ZnO hollow microspheres were obtained by controlling the heat treatment conditions. It lays a foundation for hydrothermal preparation of RF gel microspheres and its application in biological monosaccharide.
【学位授予单位】：哈尔滨工业大学
【学位级别】：博士
【学位授予年份】：2010
【分类号】：TB383.1

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