碳基纳米材料结构设计与调控及其电化学性能研究

发布时间：2018-01-09 18:27

本文关键词：碳基纳米材料结构设计与调控及其电化学性能研究　出处：《山东大学》2017年硕士论文　论文类型：学位论文

【摘要】：超级电容器作为一种重要的能源存储技术,具有锂离子电池和普通电解电容器不具备的诸多优点。目前超级电容器实现更大规模的应用主要障碍是其能量密度相对较低和制作成本较高,因此,该领域致力于提高能量密度和降低制作成本。商用超级电容器的电极材料主要是碳基材料。碳基超级电容器存在的主要问题是:居高不下的制备成本,制约了它的应用范围;而其孔径分布不合理导致的容量难以提高,则是碳基电容器电极材料制备的瓶颈。使用丰富的可再生资源制备孔隙结构可调的碳纳米材料是一种有效的降低超级电容器成本的方法。通过对碳基超级电容器材料的孔径级配和孔隙结构的设计,尝试不同方法对碳基材料进行结构调控,以研究不同碳基纳米结构对碳基超级电容器电化学储能性能的影响是本文研究的研究目标。本论文主要研究内容如下:1、以柠檬酸为原料通过冰模板法制备多孔碳气凝胶,以KOH作为活化剂进行高温活化处理,腐蚀活化出更多微孔,实现了对分级多孔的碳气凝胶的可控制备。液氮快速冷冻得到的最终样品具有圆柱形大孔,而冰箱慢速冷冻得到的最终样品具有狭缝形大孔结构。冷冻方式不同可以得到不同孔型的碳气凝胶。液氮和冰箱冷冻碳气凝胶,在2mV/s的扫速下比电容分别达到204.3 Fg-1和235.6 Fg-1。两种冰模板制备方法简单环保,为利用可再生资源制备分级多孔碳电极材料提供了一种新的制备方法。2、尽管利用冰模板法可以制备出具有良好电化学性能的多孔碳,但是制备的多孔碳的孔隙结构可控性需进一步提高。本论文首次提出将KIT-6和氧化硅球组装在一起构成二氧化硅双模板。利用结构设计和尺寸优化制备出的二氧化硅双模板,通过木素磺酸盐灌注、高温碳化、模板去除和化学活化等过程实现多孔碳孔隙结构的优化,制备出电容性能良好的分级多孔碳材料。木素磺酸盐这种天然高分子材料是非常理想的模板法制备多孔碳的原材料。本研究为利用可再生资源制备具有结构可调的多孔碳材料提供了一种有效可行的设计思路。3、在进行碳材料结构调控的基础上,设计了无机纳米结构-碳复合结构电极材料。用尿素做形态导向,通过一步水热法制备TiO2,所得TiO2在NH3气氛下800℃氮化1h。之后,葡萄糖水热法涂覆薄层碳。最后,在管式炉中800℃的NH3气氛下1h同时经历了进一步的氮化和完全碳化,转化为包碳TiN。由于TiN优异的导电性,制备成超级电容器电极后活性材料海胆状包碳TiN和基板之间具有的很好的导电接触。碳壳可以保护多晶TiN不受机械开裂和化学氧化的影响。薄层碳壳可以提高TiN的稳定性。综上所述,本论文的研究内容主要是碳基纳米材料的结构设计与调控。基于冰模板法制备碳气凝胶,通过对冷却条件的精确调控,得到不同孔型的多孔碳气凝胶,活化进一步提高了电容性能。以工业和生活废弃物提取的天然高分子为主要原料,通过二氧化硅双模板法对碳孔隙结构及其相关电学特性的调控,得到分级多孔碳电极材料。探索了碳壳包覆TiN纳米结构的构建。论文从性能设计,化学合成和结构调控,以及将不同电容器材料复合,进行了深入的理论和实验研究,并获得了高性能的超级电容器电极材料。本论文所述的研究结果和设计思路为制备高性能低成本的超级电容器碳材料提供了很好的参考。对低成本高性能电极材料的设计和制备具有重要的参考价值。
[Abstract]:The super capacitor as an important energy storage technology has many advantages of lithium ion batteries and ordinary electrolytic capacitors with super capacitor application. The main obstacle is the larger energy density is relatively low and the production cost is high, therefore, this field is committed to improving the energy density and reduce production cost. The electrode material of super capacitor is the main commercial carbon based materials. The main problems of carbon based supercapacitor is: high preparation cost, restrict its application range; and the pore size distribution of the capacity to improve, it is the bottleneck of carbon based capacitor electrode material prepared by use of renewable. Resource preparation with adjustable pore structure of carbon nano materials rich is an effective method to reduce the cost of the super capacitor. The carbon based supercapacitor material gradation and aperture The design of the pore structure, try a different method of structure regulation on carbon based materials, affect the performance of carbon based supercapacitor storage in different carbon based nano structure research object of this thesis is to study. The main contents of this dissertation are as follows: 1, raw material by ice template synthesis of porous carbon aerogels with lemon acid, with KOH as activation agents were activated at high temperature, corrosion activated more micropores, the carbon aerogel on the hierarchical porous controllable preparation. The final sample obtained with liquid nitrogen to freeze cylindrical hole, and the final sample refrigerator slow freezing has been slit shaped pore structure in different ways can be frozen. Carbon aerogels with different pass. Liquid nitrogen and carbon aerogels in the freezer, sweep speed 2mV/s specific capacitance was 204.3 Fg-1 and 235.6 Fg-1. two ice template preparation method is simple and environmental protection, The use of renewable resources for the preparation of hierarchical porous carbon electrode material provides a new method for the preparation of.2, although the use of ice template method can prepare porous carbon with excellent electrochemical properties of porous carbon, but by the controllable pore structure need to be further improved. This paper first introduces KIT-6 and silicon oxide the ball assembled together to form silica silica prepared by double template. The structure design and size optimization for double template, through high temperature carbonization, lignosulfonate perfusion, optimize the pore structure of porous carbon template removal and chemical activation process, preparation of hierarchical porous carbon materials good capacitive properties. This kind of natural polymer materials of lignosulfonate raw material is the ideal template preparation of porous carbon. This study provides a use of renewable resources for preparation of porous carbon materials with adjustable structure Effective and feasible design method of.3, based on the structure of carbon material control, the design structure of inorganic nano carbon composite electrode material with urea. The structure morphology of TiO2 oriented, prepared by one step hydrothermal method, then the TiO2 under NH3 atmosphere at a temperature of 800 DEG C nitride 1h., hydrothermal method thin layer of carbon coated glucose. Finally, in the tube furnace in 800 DEG C under NH3 atmosphere 1H also experienced further nitridation and carbonization, converted to carbon coated TiN. due to conductive TiN excellent, preparation of super capacitor electrode active material urchinlike package between carbon TiN and substrate with conductive contact is very good. The carbon shell can the protection of polycrystalline TiN is not affected by mechanical cracking and chemical oxidation. The thin carbon shell can improve the stability of the TiN. In summary, the main contents of the dissertation is the design of the structure and regulation of carbon nano materials. The preparation of carbon aerogel template method based on ice Through the precise control of the cooling conditions, the obtained porous carbon aerogels with different hole type, activation to further improve the capacitance performance. Natural polymer extracted by industrial and domestic waste as the main raw material, the regulation characteristics of carbon pore structure and its related power through silica double template method, get the hierarchical porous carbon electrode materials are discussed. The carbon shell construction of TiN nanostructures. The performance design, chemical synthesis and structure regulation, and the composite of different capacitor materials, theoretical and experimental researches were carried out, and obtained a super capacitor electrode material with high performance. The research results and the design ideas of this paper provide a good the reference for the preparation of high performance and low cost of the super capacitor carbon materials. The design and production of low cost and high performance electrode material prepared has important reference value.

【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;TM53

【相似文献】