基于卤虫卵壳的碳材料的制备及其超级电容器电化学性能的研究

发布时间：2018-12-09 19:28

【摘要】：超级电容器是一种具有广阔应用前景的储能器件。碳材料作为超级电容器的电极材料具有无污染、低成本、原料充足和电化学性能优良等诸多优点。本课题采用了一种天然生物材料卤虫卵壳作为合成碳材料的前驱体，利用在惰性保护气体下高温裂解的方式获得碳材料。研究了在不同惰性气氛中碳材料的电化学性能，酸处理对碳材料的影响。以及用KOH对碳材料在高温下进行化学活化，找出合成电化学性能良好的碳电极材料。采用X射线衍射仪(XRD)、比表面积分析（BET）、场发射扫描电镜(FE-SEM)、透色电镜（TEM）、电子能谱仪（XPS）、循环伏安法(CV)、恒电流充放电测试方法对产品进行表征。氩气气氛中制得的多级孔道碳材料，经过HNO3清洗之后，其比表面积420m2g-1，孔体积为0.258cm3g-1。并且表现出了良好的电化学性能，在1M H2SO4电解液中，最大比电容达到321F g-1，在6M KOH电解液中最大比电容达到231F g-1，在1M Na2SO4电解液中最大比电容达到了178F g-1，在6M KOH，1M H2SO4和1M Na2SO4表现出了优秀的循环性能，在电流密度5Ag-1进行充放电一万次后的容量保持率分别为100%，100%，97%。碳材料在氩气和氮气中活化的最佳条件为：Mc：MKOH=1：2（碳材料和氢氧化钾质量比），在此比例下氮气中的碳材料的比表面积达到了1256m2g-1，孔体积为0.68cm3g-1；而在此比例下氩气中的碳材料的比表面积达到了1758m2g-1，孔体积为0.76cm3g-1。在氩气中得到的电化学性能最好的多孔碳材料，在1M H2SO4电解液中，最大比电容达到369F g-1，在6M KOH电解液中最大比电容达到349F g-1，在1MNa2SO4电解液中最大比电容达到了238F g-1。将的合成的电化学性能最好的卤虫卵壳活化碳材料作为负极材料，合成的MnO2/GO作为正极材料组装非对称超级电容器，电化学测试表现出了优秀的电化学性能，电压窗口最高能到达2V，，在功率密度为100W kg-1时最大能量密度达到了46.47Wh kg-1，循环4000圈后的容量保持率为92.7%。
[Abstract]:Supercapacitor is a kind of energy storage device with wide application prospect. Carbon materials as electrode materials for supercapacitors have many advantages, such as no pollution, low cost, sufficient raw materials and excellent electrochemical performance. In this paper, a natural biological material, Artemia egg shell, was used as the precursor of synthetic carbon material, and the carbon material was obtained by pyrolysis at high temperature under inert protection gas. The electrochemical properties of carbon materials in different inert atmospheres and the effect of acid treatment on carbon materials were studied. The carbon materials were chemically activated by KOH at high temperature to find out the carbon electrode materials with good electrochemical properties. Analysis of (BET), Field Emission scanning Electron Microscopy (FE-SEM) by X-ray diffractometer (XRD), and (XPS), cyclic voltammetry (CV), by (TEM), Electron Spectrometer The product was characterized by constant current charge-discharge test. After HNO3 cleaning, the surface area and pore volume of multistage porous carbon materials prepared in argon atmosphere were 420 m2g-1 and 0.258cm3g-1, respectively. The maximum specific capacitance reached 321F g-1 in 1m H2SO4 electrolyte, 231F g-1 in 6m KOH electrolyte and 178F g-1in 1m Na2SO4 electrolyte. At 6 M KOH,1M H2SO4 and 1 M Na2SO4, excellent cycling performance is shown. After charging and discharging 10 000 times at the current density 5Ag-1, the capacity retention rate is 100m / 100g / 97, respectively. The optimum conditions for the activation of carbon materials in argon and nitrogen are as follows: Mc:MKOH=1:2 (mass ratio of carbon materials to potassium hydroxide), the specific surface area of carbon materials in nitrogen reaches 1256m2g-1, and the pore volume is 0.68cm3g-1; The specific surface area and pore volume of carbon materials in argon are 1758m2g-1and 0.76cm3g-1respectively. The porous carbon material with the best electrochemical performance in argon has the maximum specific capacitance of 369F g-1 in 1m H2SO4 electrolyte and 349F g-1 in 6m KOH electrolyte. The maximum specific capacitance reached 238 F g -1 in 1MNa2SO4 electrolyte. The synthesized halogen egg shell activated carbon material was used as negative electrode material, and the synthesized MnO2/GO was used as positive electrode material to assemble asymmetric supercapacitor. The electrochemical test showed excellent electrochemical performance. The maximum energy of the voltage window reaches 2V and the maximum energy density reaches the capacity retention rate of 92.7 after 4000 cycles of 46.47Wh kg-1, cycle when the power density is 100W kg-1.
【学位授予单位】：燕山大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：TM53;O613.71

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