本文選題：多孔炭 + 碳復(fù)合材料�。� 參考：《大連理工大學(xué)》2014年博士論文

【摘要】：超級電容器是人們廣泛關(guān)注的一種新型的儲能器件,具有功率密度高、循環(huán)壽命長等特點(diǎn)。多孔炭是目前廣為使用的一種超級電容器電極材料,其微觀形貌、比表面積、孔隙結(jié)構(gòu)、導(dǎo)電性以及表面化學(xué)性質(zhì)等均對電化學(xué)性能有著重要的影響。目前多孔炭電極材料除了能量密度較低之外,還因其結(jié)構(gòu)特點(diǎn)存在倍率性能較差的缺點(diǎn),進(jìn)而限制了材料的高功率特性。本文旨在通過改善或者優(yōu)化材料的孔隙結(jié)構(gòu)、導(dǎo)電性和微觀形貌,制備具有高倍率性能的多孔炭電極材料。 以非離子表面活性劑P123為軟模板,果糖為碳源,磷酸為磷源,耦合水熱及熱處理技術(shù)制備了具備多級孔結(jié)構(gòu)的磷修飾碳納米管／碳復(fù)合材料。適量的碳納米管有利于增加復(fù)合材料的介孔和大孔孔容,并提高復(fù)合材料的導(dǎo)電性。與不含碳納米管的材料相比,復(fù)合材料在10Ag-1的電流密度下電容保持率從6%提高到了78%。含磷官能團(tuán)可使復(fù)合材料的操作電壓提高至1.2V,并在該電壓下保持優(yōu)異的循環(huán)穩(wěn)定性。 以氧化石墨烯(GO)輔助氨基葡萄糖水熱反應(yīng)制備了高氮含量(10wt.%)的石墨烯／水熱碳復(fù)合材料；GO可誘導(dǎo)氨基葡萄糖的水熱中間物在其表面聚集而傾向形成片狀結(jié)構(gòu)。適量的石墨烯有利于水熱碳復(fù)合材料的KOH活化過程,使產(chǎn)物具有更高的比表面積、微孔和介孔孔容,導(dǎo)電性也有3個(gè)數(shù)量級的顯著提高。與不含石墨烯的材料相比,復(fù)合材料具有更高的比電容值(300F g-1)以及更好的倍率性能,在8Ag-1的電流密度下電容保持率由36%提高到了76%。 以多巴胺為碳源,利用其在堿性有氧環(huán)境下的自聚特性,在納米碳酸鈣表面聚合了超薄聚多巴胺層。經(jīng)熱處理聚多巴胺層可轉(zhuǎn)變?yōu)槌√紝?同時(shí)納米碳酸鈣分解產(chǎn)生的二氧化碳可原位活化碳層引入微孔,除去模板后可得到類石墨烯結(jié)構(gòu)的二維超薄多孔碳納米片。電化學(xué)測試結(jié)果表明超薄多孔碳納米片具有優(yōu)異的倍率性能,在高達(dá)100Ag-1的電流密度下具有71%的電容保持率。 以具有層狀納米空間的蒙脫土為限域模板,明膠和多巴胺為代表碳源,利用二者之間的插層反應(yīng)構(gòu)建了制備二維碳納米片的通用方法,對碳納米片進(jìn)一步KOH活化處理可得多孔碳納米片電極材料�；诿髂z的多孔碳納米片在高達(dá)100Ag-1的電流密度下比電容可達(dá)246Fg-1,電容保持率與明膠直接預(yù)炭化活化的產(chǎn)物相比由44%提高到82%。兩電極體系下明膠基多孔碳納米片在水系和有機(jī)系電解液中也均具有優(yōu)異的倍率性能,在40Ag-1的電流密度下電容保持率分別可達(dá)83和81%。
[Abstract]:Supercapacitor is a new type of energy storage device, which has high power density and long cycle life. Porous carbon is a widely used electrode material for supercapacitors. Its micro-morphology, specific surface area, pore structure, conductivity and surface chemical properties all have important effects on electrochemical properties. In addition to the low energy density, the porous carbon electrode materials have the disadvantage of poor rate performance due to their structural characteristics, which limits the high power characteristics of the materials. The aim of this paper is to prepare porous carbon electrode materials with high rate properties by improving or optimizing the pore structure, electrical conductivity and micromorphology of the materials. Using Nonionic surfactant P123 as soft template, fructose as carbon source and phosphoric acid as phosphorus source, phosphorous modified carbon nanotubes / carbon composites with multilevel pore structure were prepared by coupled hydrothermal and heat treatment techniques. The proper amount of carbon nanotubes can increase the mesoporous and large pore volume of the composites and improve the conductivity of the composites. Compared with the materials without carbon nanotubes, the capacitance retention rate of the composites increased from 6% to 78% at the current density of 10Ag-1. Phosphorus-containing functional groups can increase the operating voltage of the composite to 1.2 V and maintain excellent cyclic stability at this voltage. A graphene / hydrothermal carbon composite with high nitrogen content (10 wt.) was prepared by hydrothermal reaction of glucosamine with graphene oxide (GOO), which can induce the hydrothermal intermediates of glucosamine to aggregate on its surface and tend to form a flake structure. Proper amount of graphene is propitious to the Koh activation process of hydrothermal carbon composites, which makes the products have higher specific surface area, micropore and mesoporous volume, and the electrical conductivity is improved by three orders of magnitude. Compared with the materials without graphene, the composite has higher specific capacitance value (300F g-1) and better rate performance. At the current density of 8Ag-1, the capacitance retention rate is increased from 36% to 76%. Using dopamine as carbon source, ultrathin polydopamine layer was polymerized on the surface of nanometer calcium carbonate by using its self-polymerization property in alkaline aerobic environment. After heat treatment, the polydopamine layer can be transformed into ultrathin carbon layer, and the carbon dioxide generated by the decomposition of nano-calcium carbonate can be activated in situ and introduced into micropores. After removing the template, two-dimensional ultrathin porous carbon nanochips with graphene like structure can be obtained. The electrochemical test results show that ultrathin porous carbon nanochips have excellent rate performance and have a capacitance retention rate of 71% at current density up to 100Ag-1. Using montmorillonite with layered nanospace as the limiting template and gelatin and dopamine as the representative carbon source, a general method for preparing two-dimensional carbon nanochips was constructed by intercalation reaction between them. Porous carbon nanochip electrode materials can be obtained by further Koh activation treatment of carbon nanochips. The specific capacitance of porous carbon nanoparticles based on gelatin can reach 246Fg-1 at current density up to 100Ag-1, and the capacitance retention rate is increased from 44% to 82% compared with the products directly precarbonated by gelatin. In the two-electrode system, gelatine-based porous carbon nanochips also have excellent rate performance in aqueous and organic electrolyte systems, and the capacitance retention rates can reach 83 and 81 at the current density of 40Ag-1, respectively.
【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TQ127.11;TM53

【共引文獻(xiàn)】

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本文編號：2013744