本文關(guān)鍵詞： 超級電容器 碳基電極材料 乙二胺四乙酸三鉀鹽(EDTA-3K) 自活化 摻雜 電化學(xué)性能　出處：《江蘇大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：隨著能源危機加劇和環(huán)境問題日益突出,迫切需要開發(fā)綠色環(huán)保、性能卓越的儲能裝置。超級電容器作為一種新型儲能元件,具有能量密度和功率密度高、循環(huán)壽命長、環(huán)境友好等特性,是理想的儲能系統(tǒng),因此開發(fā)超級電容器具有重要的理論意義和應(yīng)用價值。超級電容器性能的優(yōu)劣主要取決于所用的電極材料。多孔碳及其復(fù)合材料,因其具有物化性質(zhì)穩(wěn)定、循環(huán)性能好、環(huán)保無污染等特點,被廣泛用作超級電容器電極材料。如何簡單可控地制備高性能多孔碳基電極材料仍然是當前面臨的挑戰(zhàn)之一。本論文圍繞如何提高超級電容器電極材料的性能展開,提出利用富氮有機鉀鹽為碳源,一步自活化制備摻雜型多孔碳材料,同時與模板限域法、微波法、水熱法等相結(jié)合,對其孔結(jié)構(gòu)調(diào)控和復(fù)合改性,獲得了一系列高比電容的新型多孔碳基電極材料。采用多種表征技術(shù)對形貌特征、孔隙結(jié)構(gòu)、組成成分、結(jié)晶性等進行測試,利用循環(huán)伏安、恒電流充放電、交流阻抗等方法測試其電化學(xué)性能,篩選和構(gòu)建高性能超級電容器用多孔碳基電極材料體系。主要研究工作如下:(1)以EDTA-3K為碳源,通過一步煅燒法,利用分子內(nèi)含氮、氧以及羧酸鉀,自活化原位摻雜制備了高比表面積氮氧雙摻雜多級孔碳材料EPCs-T。探討不同煅燒溫度的影響,發(fā)現(xiàn)氮氧含量隨溫度升高而減少,孔體積和孔徑隨溫度增加而增大,EPCs-800擁有最高比表面積,達到2787 m~2 g~(-1),同時,EPCs-800的比電容性能最好,電流密度為1 A g~(-1)時比電容為182.3 F g~(-1),在電流密度5 A g~(-1)下經(jīng)過2000次循環(huán)之后比電容能夠保持最初的95.2%,說明該超級電容器電極材料具有較好的充放電穩(wěn)定性。(2)以EDTA-3K為碳源,SBA~(-1)5為硬模板,通過限域碳化制備摻雜型多級孔碳材料SEPCs-T。探討煅燒溫度對其孔隙結(jié)構(gòu)、組成成分等理化性質(zhì)及電容性能的影響。表征結(jié)果表明SEPCs-T呈現(xiàn)清晰海綿狀結(jié)構(gòu),微孔比表面積隨煅燒溫度升高而減小,而孔體積和孔徑尺寸隨煅燒溫度升高而增大,SEPCs-800比表面積最高(2578 m~2 g~(-1))。同條件下,SEPCsT的氧/氮含量與上章節(jié)制備的EPCs-T并沒有明顯差異。SEPCs-700的電化學(xué)性能最好,在電流密度為1 A g~(-1)時比電容為213.8 F g~(-1)。SEPCs-T含有大量介/大孔結(jié)構(gòu),提供有效的離子傳輸通道促進離子遷移和儲存,有助于提升電極材料電化學(xué)性能,進而比電容值高于EPCs-T。(3)以EPCs-800為載體,采用恒溫水浴和微波輻射法兩種不同加熱方式,通過尿素均勻沉淀法和低溫氧化法相結(jié)合在EPCs-800表面生長雙金屬氧化物NiCo_2O_4納米片,制備出EPCs-800/NiCo_2O_4復(fù)合電極材料,來增加贗電容,提高電化學(xué)性能。兩種加熱方式都可以使NiCo_2O_4成功地負載于EPCs-800多孔碳表面,但是其生長取向有所不同。傳統(tǒng)水浴加熱制備的NiCo_2O_4平行于碳表面方向上生長;而微波輻射法制備的NiCo_2O_4垂直于碳表面生長,且更加均勻、致密。電化學(xué)結(jié)果:電流密度為1 A g~(-1)時,EPCs-800/NiCo_2O_4~(-1)和EPCs-800/NiCo_2O_4-2電極材料的比電容值分別為207.6和434.8 F g~(-1),并且EPCs-800/NiCo_2O_4-2電極擁有更好的倍率性能、循環(huán)性能和更低的電阻。(4)以硝酸鈷為金屬源,尿素為堿源和氮源,EDTA-3K為碳、氮源及活化劑,同時摻入石墨烯納米片,采用水熱法、高溫煅燒法和低溫氧化法相結(jié)合,制備出四氧化三鈷/石墨烯納米片/碳三元多級結(jié)構(gòu)復(fù)合電極材料(Co_3O_4/GNS/EPCs)。表征測試結(jié)果顯示,石墨烯納米片起到結(jié)構(gòu)導(dǎo)向與模板調(diào)控作用,同時EDTA-3K又可以自活化和同步活化石墨烯,被插層的EDTA-3K源多孔碳與活化的石墨烯納米片一起構(gòu)成復(fù)合碳納米片層結(jié)構(gòu),促使Co_3O_4納米顆粒高度分散,避免了相互堆疊。此外,加入石墨烯很大程度地提升了復(fù)合材料導(dǎo)電性。電化學(xué)性能測試顯示Co_3O_4/GNS/EPCs電極材料在電流密度為1 A g~(-1)時比電容達到772.4 F g~(-1),遠高于純碳材料EPCs-T,同時具有很好的倍率特性、循環(huán)性能以及低的阻抗。優(yōu)良的電化學(xué)特性可能歸因于活化的導(dǎo)電石墨烯層、多孔碳、Co_3O_4納米顆粒以及氮氧元素摻雜四者之間協(xié)同作用的結(jié)果。
[Abstract]:With the aggravation of energy crisis and environmental problems have become increasingly prominent, urgent need for the development of green environmental protection, excellent performance of the super capacitor energy storage device. As a new type of energy storage device with energy density and high power density, long cycle life, environmental friendliness, is the ideal energy storage system, so the development of super capacitor with the important theoretical significance and application value. The merits of super capacitor performance mainly depends on the electrode materials used. Porous carbon and its composite materials, because of its stable physicochemical property, good cycle performance, no environmental pollution and other characteristics, are widely used as electrode material for supercapacitor. How simple and controllable preparation of carbon high performance porous electrode material is still one of the current challenges. This paper focuses on how to improve the performance of the super capacitor electrode material, the nitrogen rich organic potassium as a carbon source. Step self doped porous carbon materials and activation, confinement and template method, microwave method combined with hydrothermal method, the pore structure control and composite modification, obtain a series of high specific capacitance of porous carbon based electrode materials. Using a variety of characterization techniques on morphology, pore structure and composition to test the composition, crystallinity, by cyclic voltammetry, galvanostatic charge discharge and AC impedance method to test its electrochemical performance, selection and construction of high performance supercapacitors using porous carbon based electrode system. The main research work is as follows: (1) using EDTA-3K as carbon source, through one step sintering method, using molecular nitrogen, oxygen and potassium carboxylate, since activation in situ doping were prepared with high specific surface area for oxygen and nitrogen doped hierarchicalporous carbon material EPCs-T. to investigate the effects of different calcination temperature, found that the content of nitrogen and oxygen decreases as the temperature increases, the pore volume and pore size with temperature Increases, EPCs-800 has the highest surface area, up to 2787 m~2 g~ (-1), at the same time, EPCs-800 had better than capacitive performance, current density of 1 A g~ (-1) when the specific capacitance of 182.3 F g~ (-1), at a current density of 5 A g~ (-1) after 2000 cycle the capacitance can keep the original 95.2%, indicating that the electrode material of super capacitor charge and discharge with a good stability. (2) using EDTA-3K as carbon source, SBA~ (-1) 5 as hard templates were prepared by doped hierarchicalporous carbon materials SEPCs-T. study on the pore structure of the calcination temperature limit domain carbonization, influence of composition the physicochemical properties and capacitance performance. The characterization results show that SEPCs-T presents a clear spongy structure, micropore surface area with the calcination temperature increasing, the pore volume and pore size increased with the calcination temperature increasing, the specific surface area of the highest SEPCs-800 (2578 m~2 g~ (-1)). Under the same condition, the oxygen SEPCsT / The electrochemical performance and nitrogen content of the chapters prepared EPCs-T and no significant difference of the.SEPCs-700 best, at a current density of 1 A g~ (-1) when the specific capacitance of 213.8 F g~ (-1).SEPCs-T contains a large number of medium / large pore structure, provide ion transfer channels effectively promote ion transport and storage, help enhance the electrochemical performance of electrode materials, and the specific capacitance is higher than that of EPCs-T. (3) with EPCs-800 as the carrier, with constant temperature water bath and microwave radiation by two different heating methods, the growth of double metal oxide NiCo_2O_4 nano film on the surface of EPCs-800 by urea homogeneous precipitation method and low-temperature oxidation method, preparation of EPCs-800/NiCo_2O_4 composite electrode materials to increase pseudocapacitive, improve the electrochemical performance. Two kinds of heating methods can make NiCo_2O_4 successfully loaded on EPCs-800 porous carbon surface, but its growth orientation is different. The traditional water bath heating preparation The growth of NiCo_2O_4 is parallel to the direction of carbon on the surface; and the microwave radiation preparation of NiCo_2O_4 perpendicular to the surface of carbon growth, and more uniform and compact. The electrochemical results: current density of 1 A g~ (-1), EPCs-800/NiCo_2O_4~ (-1) and EPCs-800/NiCo_2O_4-2 electrode specific capacitance values were 207.6 and 434.8 F g~ (-1), and rate performance of EPCs-800/NiCo_2O_4-2 electrode has better performance and lower resistance, cycle. (4) using cobalt nitrate as metal source, alkali source and urea as nitrogen source, EDTA-3K carbon, nitrogen source and activator, and the incorporation of graphene nanosheets by hydrothermal method, the combination of high temperature calcination method and low temperature oxidation, prepared four oxidation three cobalt / graphene nanosheets / carbon composite electrode material three yuan multistage structure (Co_3O_4/GNS/EPCs) characterization. The testing results show that the graphene nanosheets to guide and regulate the template structure, and at the same time EDTA-3K Self activation and synchronous live graphene, EDTA-3K source porous carbon intercalation and graphene nanosheets activated carbon nano composite composed of lamellar structure, the highly dispersed Co_3O_4 nanoparticles, avoid overlapping. In addition, addition of graphene greatly improves the conductivity of the composite material. The electrochemical performance of test shows that the electrode materials of Co_3O_4/GNS/EPCs at a current density of 1 A g~ (-1) is a specific capacitance of 772.4 F g~ (-1), much higher than that of pure carbon material EPCs-T, and has very good rate performance, cycle performance and low electrical impedance. Excellent chemical properties may be attributed to the conductive graphene layer, porous activated carbon, nitrogen and oxygen between Co_3O_4 nanoparticles and doping the synergy of the four results.

【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TB332;TM53

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