本文關(guān)鍵詞：基于固廢高分子材料制備多孔炭材料及其電化學(xué)性能研究　出處：《江蘇大學(xué)》2015年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 固廢高分子材料 資源化利用 納米多孔炭 電化學(xué)性能 模板炭化法 超級(jí)電容器

【摘要】：固廢高分子材料的資源化再利用是亟待解決的問題,也是當(dāng)前研究的熱點(diǎn)。本論文以不同固廢高分子材料為原料制備納米多孔炭材料,研究炭材料的可控合成及其電化學(xué)性能,以應(yīng)用于超級(jí)電容器,為廢舊高分子材料的資源化利用提供新途徑。論文以聚四氟乙烯、聚氯乙烯、聚偏氟乙烯、聚對(duì)苯二甲酸乙二醇酯、乙二胺四乙酸二鈉鹽配合物等固廢高分子材料為原料和CaCO3、Ca(OAc)2、2檸檬酸鎂、Mg(OH)2等為模板劑,采用模板炭化法制備一系列納米多孔炭材料,選擇XRD、FESEM、HRTEM、Raman、XPS等技術(shù)手段對(duì)炭材料的結(jié)構(gòu)進(jìn)行表征,選用三電極系統(tǒng)對(duì)其電化學(xué)性能進(jìn)行測(cè)試,包含CV曲線、充放電曲線、循環(huán)穩(wěn)定性、Nyquist圖等。論文的主要研究?jī)?nèi)容如下：1.以聚四氟乙烯(PTFE)固廢材料為原料,采用CaCO3協(xié)同模板炭化法研制納米多孔炭材料,并研討其電化學(xué)特性。結(jié)果表明,PTFE與CaCO3之間的質(zhì)量比,以及炭化溫度決定著炭材料的孔結(jié)構(gòu)。在PTFE與CaCO3質(zhì)量比為2：1、炭化溫度為700℃的條件下得到的炭材料樣品(標(biāo)記為carbon-2:1)具有良好的多孔特性,其總孔容為0.65 cm3 g-1, BET比表面積為646.3 m2g-1。在6 mol L-1 KOH溶液為電解液的三電極系統(tǒng)中,在電流密度為1Ag-1時(shí),樣品的質(zhì)量比電容可達(dá)179.9F g-1。在此基礎(chǔ)上,為了更好地調(diào)控carbon-2:1樣品的孔結(jié)構(gòu)和電化學(xué)性能,在反應(yīng)體系中加入了適量的CO(NH2)2物質(zhì),在PTFE、CaCO3與CO(NH2)2質(zhì)量比為2：1：2、炭化溫度為700℃的條件下得到炭材料樣品(標(biāo)記為carbon-2：1：2),該樣品的BET比表面積更大,達(dá)1048.2 m2g-1,總孔容更高,達(dá)到1.03 cm3g-1,在電流密度為1 A g-1時(shí),該樣品的比電容也提升到237.8F g-1。本論文提出的CaCO3模板炭化法具有簡(jiǎn)單、高效、可重復(fù)性高以及易于工業(yè)化生產(chǎn)等特點(diǎn),可應(yīng)用于含鹵體系固廢高分子材料的資源化利用。2.以聚對(duì)苯二甲酸乙二醇酯(PET)固廢材料為原料,采用Ca(OAc)2H2O為硬模板,炭化法制備納米多孔炭材料,研究其電化學(xué)性能。實(shí)驗(yàn)結(jié)果表明,PET固廢與Ca(OAC)2H2O之間的質(zhì)量比對(duì)于炭材料的多孔結(jié)構(gòu)和電化學(xué)性能有著重要的影響。在PET與Ca(OAC)2-H2O質(zhì)量比為3：1、炭化溫度為800℃的條件下得到的炭材料樣品(標(biāo)記為carbon-3:1),具有較好的多孔特性,其BET比表面積為749.6m2g-1、總孔容為0.52 cm3g-1。在6 mol L-1 KOH溶液為電解液的三電極體系中,該樣品在電流密度為1 A g-1時(shí)的質(zhì)量比電容可達(dá)到402.2 F g-1,在電流密度增大到40 A g-1時(shí),相應(yīng)的質(zhì)量比電容可保持172 Fg-1。此外,該carbon-3:1樣品經(jīng)過5000次循環(huán)后比電容仍可以保持96.05%,顯示出優(yōu)良的循環(huán)穩(wěn)定性。因此,Ca(OAC)2-H2O輔助模板炭化法可以用于聚酯廢舊塑料制備超級(jí)電容器中的多孔炭材料。3.采用檸檬酸鎂為硬模板,以聚偏氟乙烯(PVDF)、聚氯乙烯(PVC)、聚四氟乙烯(PTFE)等固廢材料為原料,炭化法制備相應(yīng)納米多孔炭材料,對(duì)其在超級(jí)電容器中的電化學(xué)性能進(jìn)行研究。在炭化溫度為700℃下,固定PTFE、PVC、PVDF與檸檬酸鎂的質(zhì)量比為1：1,即可制備出FTFE-1:1-700、PVC-1:1-700和PVDF-1:1-700三種樣品。XRD、Raman和FESEM測(cè)試表明該系列炭材料樣品均呈現(xiàn)出典型的非晶態(tài)特征,且具有納米尺寸形態(tài)。N2吸附-脫附測(cè)試結(jié)果表明,BET比表面積和總孔容的大小順序?yàn)椋篜VDF-1:1-700PVC-1:1-700PTFE-1:1-700,且PVDF-1:1-700樣品的BET比表面積可達(dá)668.3 m2g-1、總孔容為0.60 cm3g-1,顯示出較好的多孔性能。以6 mol L_1KOH作為電解液,使用三電極系統(tǒng),室溫下在超級(jí)電容器中測(cè)定炭材料樣本的電化學(xué)性能,結(jié)果提示,在電流密度為1Ag-1下,PTFE-1:1-700、PVC-1:1-700和PVDF-1:1-700樣品的質(zhì)量比電容分別可以達(dá)到33.5 Fg-1、31.7 Fg-1和89.6 Fg-1,其中PVDF-1:1-700樣品具有最高的比電容數(shù)值。因此,檸檬酸鎂輔助模板炭化法具有簡(jiǎn)單、高效、低污染、可規(guī)�；a(chǎn)等優(yōu)點(diǎn),可以用來資源化利用廢舊塑料。4.利用固廢乙二胺四乙酸鎂配合物為炭源／氮源,Mg(OH)2為模板劑,通過模板炭化法制備氮摻雜的納米多孔炭材料,并進(jìn)行超級(jí)電容器領(lǐng)域中的電化學(xué)性能研究。實(shí)驗(yàn)結(jié)果表明,引入Mg(OH)2可以顯著改變炭材料樣品的孔結(jié)構(gòu),并有效提升其電化學(xué)性能。直接在800℃下炭化乙二胺四乙酸鎂配合物與Mg(OH)2(質(zhì)量比為1：3),得到的樣品(標(biāo)記為carbon-1:3-800)的BET比表面積大,達(dá)到766.8 m2g-1,總孔容高,達(dá)1.16 cm3g-1,氮含量為9.48%。在6 mol L-1 KOH溶液為電解液的三電極測(cè)試體系中,carbon-1:3-800樣品在電流密度為1 Ag-1時(shí)的質(zhì)量比電容為367.5 F g-1,而且在高電流密度1 A g-1時(shí)的倍率性能為47.3%。因此,Mg(OH)2模板炭化法可以將乙二胺四乙酸鎂配合物固廢材料成功轉(zhuǎn)化為氮摻雜的納米多孔材料,并有望應(yīng)用于超級(jí)電容器電極材料領(lǐng)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.

【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ127.11;X705

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本文編號(hào)：1418876