基于固废高分子材料制备多孔炭材料及其电化学性能研究

发布时间：2018-01-13 12:47

本文关键词：基于固废高分子材料制备多孔炭材料及其电化学性能研究　出处：《江苏大学》2015年博士论文　论文类型：学位论文

【摘要】：固废高分子材料的资源化再利用是亟待解决的问题,也是当前研究的热点。本论文以不同固废高分子材料为原料制备纳米多孔炭材料,研究炭材料的可控合成及其电化学性能,以应用于超级电容器,为废旧高分子材料的资源化利用提供新途径。论文以聚四氟乙烯、聚氯乙烯、聚偏氟乙烯、聚对苯二甲酸乙二醇酯、乙二胺四乙酸二钠盐配合物等固废高分子材料为原料和CaCO3、Ca(OAc)2、2柠檬酸镁、Mg(OH)2等为模板剂,采用模板炭化法制备一系列纳米多孔炭材料,选择XRD、FESEM、HRTEM、Raman、XPS等技术手段对炭材料的结构进行表征,选用三电极系统对其电化学性能进行测试,包含CV曲线、充放电曲线、循环稳定性、Nyquist图等。论文的主要研究内容如下：1.以聚四氟乙烯(PTFE)固废材料为原料,采用CaCO3协同模板炭化法研制纳米多孔炭材料,并研讨其电化学特性。结果表明,PTFE与CaCO3之间的质量比,以及炭化温度决定着炭材料的孔结构。在PTFE与CaCO3质量比为2：1、炭化温度为700℃的条件下得到的炭材料样品(标记为carbon-2:1)具有良好的多孔特性,其总孔容为0.65 cm3 g-1, BET比表面积为646.3 m2g-1。在6 mol L-1 KOH溶液为电解液的三电极系统中,在电流密度为1Ag-1时,样品的质量比电容可达179.9F g-1。在此基础上,为了更好地调控carbon-2:1样品的孔结构和电化学性能,在反应体系中加入了适量的CO(NH2)2物质,在PTFE、CaCO3与CO(NH2)2质量比为2：1：2、炭化温度为700℃的条件下得到炭材料样品(标记为carbon-2：1：2),该样品的BET比表面积更大,达1048.2 m2g-1,总孔容更高,达到1.03 cm3g-1,在电流密度为1 A g-1时,该样品的比电容也提升到237.8F g-1。本论文提出的CaCO3模板炭化法具有简单、高效、可重复性高以及易于工业化生产等特点,可应用于含卤体系固废高分子材料的资源化利用。2.以聚对苯二甲酸乙二醇酯(PET)固废材料为原料,采用Ca(OAc)2H2O为硬模板,炭化法制备纳米多孔炭材料,研究其电化学性能。实验结果表明,PET固废与Ca(OAC)2H2O之间的质量比对于炭材料的多孔结构和电化学性能有着重要的影响。在PET与Ca(OAC)2-H2O质量比为3：1、炭化温度为800℃的条件下得到的炭材料样品(标记为carbon-3:1),具有较好的多孔特性,其BET比表面积为749.6m2g-1、总孔容为0.52 cm3g-1。在6 mol L-1 KOH溶液为电解液的三电极体系中,该样品在电流密度为1 A g-1时的质量比电容可达到402.2 F g-1,在电流密度增大到40 A g-1时,相应的质量比电容可保持172 Fg-1。此外,该carbon-3:1样品经过5000次循环后比电容仍可以保持96.05%,显示出优良的循环稳定性。因此,Ca(OAC)2-H2O辅助模板炭化法可以用于聚酯废旧塑料制备超级电容器中的多孔炭材料。3.采用柠檬酸镁为硬模板,以聚偏氟乙烯(PVDF)、聚氯乙烯(PVC)、聚四氟乙烯(PTFE)等固废材料为原料,炭化法制备相应纳米多孔炭材料,对其在超级电容器中的电化学性能进行研究。在炭化温度为700℃下,固定PTFE、PVC、PVDF与柠檬酸镁的质量比为1：1,即可制备出FTFE-1:1-700、PVC-1:1-700和PVDF-1:1-700三种样品。XRD、Raman和FESEM测试表明该系列炭材料样品均呈现出典型的非晶态特征,且具有纳米尺寸形态。N2吸附-脱附测试结果表明,BET比表面积和总孔容的大小顺序为：PVDF-1:1-700PVC-1:1-700PTFE-1:1-700,且PVDF-1:1-700样品的BET比表面积可达668.3 m2g-1、总孔容为0.60 cm3g-1,显示出较好的多孔性能。以6 mol L_1KOH作为电解液,使用三电极系统,室温下在超级电容器中测定炭材料样本的电化学性能,结果提示,在电流密度为1Ag-1下,PTFE-1:1-700、PVC-1:1-700和PVDF-1:1-700样品的质量比电容分别可以达到33.5 Fg-1、31.7 Fg-1和89.6 Fg-1,其中PVDF-1:1-700样品具有最高的比电容数值。因此,柠檬酸镁辅助模板炭化法具有简单、高效、低污染、可规模化生产等优点,可以用来资源化利用废旧塑料。4.利用固废乙二胺四乙酸镁配合物为炭源／氮源,Mg(OH)2为模板剂,通过模板炭化法制备氮掺杂的纳米多孔炭材料,并进行超级电容器领域中的电化学性能研究。实验结果表明,引入Mg(OH)2可以显著改变炭材料样品的孔结构,并有效提升其电化学性能。直接在800℃下炭化乙二胺四乙酸镁配合物与Mg(OH)2(质量比为1：3),得到的样品(标记为carbon-1:3-800)的BET比表面积大,达到766.8 m2g-1,总孔容高,达1.16 cm3g-1,氮含量为9.48%。在6 mol L-1 KOH溶液为电解液的三电极测试体系中,carbon-1:3-800样品在电流密度为1 Ag-1时的质量比电容为367.5 F g-1,而且在高电流密度1 A g-1时的倍率性能为47.3%。因此,Mg(OH)2模板炭化法可以将乙二胺四乙酸镁配合物固废材料成功转化为氮掺杂的纳米多孔材料,并有望应用于超级电容器电极材料领域。
[Abstract]:Resource waste polymer material recycling is an urgent problem to be solved, but also a research focus. In this paper, different solid polymer material as raw material to prepare porous carbon nano materials, controllable synthesis of carbon materials and their electrochemical properties, applied to the super capacitor, provide a new way for the resource utilization of waste polymer material of PVC, PTFE, PVDF, polyethylene terephthalate, two sodium EDTA complexes in solid polymer materials as raw materials and CaCO3, Ca (OAc) 2,2 citric acid magnesium, Mg (OH) 2 as a template to prepare a series of nano porous carbon materials by template carbonization method select XRD, FESEM, HRTEM, Raman, XPS and other technical means on the structure of carbon materials were characterized using three electrode system to test its electrochemical properties, including CV curve, the charge discharge curves, cyclic The stability of Nyquist map. The main contents of this thesis are as follows: 1. using polytetrafluoroethylene (PTFE) solid waste materials as raw materials, using CaCO3 collaborative template carbonization method study of nano porous carbon materials, and the study of its electrochemical properties. The results show that the quality between PTFE and CaCO3, as well as the carbonization temperature determines the pore structure of carbon materials in PTFE and CaCO3. The mass ratio of 2:1, carbon material samples obtained condition carbonization temperature is 700 DEG C under the (labeled carbon-2:1) has good characteristics of porous, the total pore volume of 0.65 cm3 g-1, BET specific surface area of 646.3 m2g-1. in 6 mol L-1 KOH solution as electrolyte in three electrode system. When the current density is 1Ag-1, the quality of the sample specific capacitance up to 179.9F g-1. on the basis of this, in order to pore structure and electrochemical performance of better control carbon-2:1 samples, adding the right amount of CO in the reaction system (NH2) in the 2 substances. PTFE, CaCO3 and CO (NH2) 2 mass ratio was 2:1:2, condition of carbonization temperature is 700 DEG C under the carbon material samples (labeled carbon-2:1:2), the BET of the sample is greater than the surface area of 1048.2 m2g-1, the total pore volume is higher, up to 1.03 cm3g-1, at a current density of 1 A g-1 the samples, the specific capacitance is also upgraded to CaCO3 237.8F g-1. template carbonization method proposed in this paper has the advantages of simple structure, high efficiency, high repeatability and easy industrialization production, can be used in halogen containing polymer system of solid waste resource utilization of.2. in polyethylene glycol two ester (PET) solid waste materials as raw materials. Using Ca (OAc) 2H2O as hard template, porous carbon nano material carbonization method, study its electrochemical properties. The experimental results show that PET and Ca (OAC) solid quality ratio between 2H2O for the porous structure and electrochemical properties of carbon materials have an important effect on PET and. Ca (OAC) 2-H2O mass ratio of 3:1, carbon material samples obtained condition carbonization temperature is 800 DEG C under the (labeled carbon-3:1), has a porous characteristic better, the BET surface area is 749.6m2g-1, the total Kong Rong is 0.52 cm3g-1. at 6 mol L-1 KOH solution for three electrode system in the electrolyte, the sample when the current density is 1 A g-1 when the quality of the specific capacitance can reach 402.2 F g-1, the current density increased to 40 A g-1, the mass ratio of capacitance can be maintained for 172 Fg-1. in the carbon-3:1 samples after 5000 cycles the specific capacitance can still maintain 96.05%, showing excellent cycle stability. Therefore, Ca (OAC) 2-H2O assisted template carbonization method can be used for the preparation of polyester waste plastic porous carbon materials.3. in super capacitor using magnesium citrate as hard template, using polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE) and other solid waste as raw material The material, to prepare nano porous carbon material carbonization method, studied in super capacitor electrochemical performance. The carbonization temperature is 700 DEG C, fixed PTFE, PVC, PVDF and the quality of magnesium citrate is 1:1, can be prepared by FTFE-1:1-700, PVC-1:1-700 and PVDF-1:1-700 in three samples of Raman and.XRD. The FESEM test showed that this series of carbon material samples showed typical characteristics of amorphous, with nanometer size and morphology of.N2 adsorption desorption test results show that the BET surface area and total pore volume order: PVDF-1:1-700PVC-1:1-700PTFE-1:1-700, PVDF-1:1-700 and BET of the sample surface area up to 668.3 m2g-1, the total Kong Rong is 0.60 cm3g-1. Show good performance in 6. The porous mol L_1KOH as electrolyte, three electrode system, room temperature determination of electrochemical properties of carbon materials, samples in super capacitor results suggest that in the current The density of 1Ag-1, PTFE-1:1-700, PVC-1:1-700 and PVDF-1:1-700 samples quality specific capacitance can reach 33.5 Fg-1,31.7 Fg-1 and 89.6 Fg-1 PVDF-1:1-700 samples, which have the highest specific capacitance value. Therefore, magnesium citrate assisted template carbonization method is simple, efficient, low pollution, large-scale production and other advantages, can be used for resource utilization the use of solid waste plastics.4. EDTA magnesium complexes as carbon source and nitrogen source, Mg (OH) 2 as a template, nano porous carbon materials by nitrogen doping by template carbonization method, and electrochemical properties of the field in super capacitor. The experimental results show that the introduction of Mg (OH) 2 can significantly change the hole the structure of carbon material samples, and effectively improve the electrochemical performance. Direct carbonization at 800 DEG C EDTA magnesium complexes with Mg (OH) 2 (mass ratio 1:3), obtained samples (labeled CA Rbon-1:3-800) BET surface area, m2g-1 reached 766.8, the total pore volume is high, up to 1.16 cm3g-1, the nitrogen content is 9.48%. in 6 mol L-1 solution of KOH three electrode test system of electrolyte, carbon-1:3-800 samples at a current density of 1 Ag-1 when the mass specific capacitance of 367.5 F g-1, and in high rate performance when the current density of 1 A g-1 47.3%. so Mg (OH) 2 template carbonization method can be EDTA magnesium complexes of solid waste materials successfully transformed into nano porous materials doped with nitrogen, and is expected to be applied in the field of super capacitor electrode material.

【学位授予单位】：江苏大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TQ127.11;X705

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