基于氧化石墨烯与豆渣的复合碳材料制备及性能表征
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摘要
以氧化石墨烯(graphene oxide,GO)和豆渣为原料,通过溶剂热反应获得了石墨烯基三维网状复合碳材料,并进一步通过高温焙烧获得导电性良好的复合碳材料。通过场发射电子显微镜、X射线衍射仪、拉曼光谱仪、元素分析仪、电化学分析仪对复合碳材料的形貌、物相、分子结构、元素组成和电化学性能进行了表征。结果表明,在GO中引入豆渣不仅可以在溶剂热和碳化过程中阻止石墨烯片层的重叠,还可以引入氮元素,该复合碳材料与纯GO或纯豆渣制备得到的碳材料相比表现出了更加优异的电化学性能。其中当GO与豆渣质量比为1∶2时,所得到的复合碳材料在1A/g的电流密度下比电容为201.9F/g,远高于纯石墨烯或纯豆渣所制备得到的碳材料比电容(分别为93和78F/g)。
Three dimensional graphene-based networks were prepared by the hydrothermal and carbonization process with graphene oxide and bean dregs.The morphology,crystalline form,molecular structure,composition of chemical elements and electrochemical performance of carbon composites were characterized by field emission scanning electron microscope(FE-SEM),X-ray diffractometer,Raman spectrometer,elemental analyzer,cyclic voltammetry,and galvanostatic charge-discharge and electrical impedance spectroscopy.The results show that the bean dregs could not only act as interlayer spacer to prevent the agglomeration of graphene layers,but also introduce the N element to the carbon composites,which could enhance the capacitance performance of the carbon composite materials.The carbon composite materials prepared under the mass ratio of 1∶2 between the graphene oxide and bean dregs exhibited the maximum specific capacitance of 201.9 F/g at a current density of 1 A/g.The specific capacitance of 1 G2 BD-HC was much higher than that for carbon materials prepared from pure bean dregs and pure graphene oxide,which were 78.0 and 93.0 F/g at a current density of1 A/g,respectively.
Three dimensional graphene-based networks were prepared by the hydrothermal and carbonization process with graphene oxide and bean dregs.The morphology,crystalline form,molecular structure,composition of chemical elements and electrochemical performance of carbon composites were characterized by field emission scanning electron microscope(FE-SEM),X-ray diffractometer,Raman spectrometer,elemental analyzer,cyclic voltammetry,and galvanostatic charge-discharge and electrical impedance spectroscopy.The results show that the bean dregs could not only act as interlayer spacer to prevent the agglomeration of graphene layers,but also introduce the N element to the carbon composites,which could enhance the capacitance performance of the carbon composite materials.The carbon composite materials prepared under the mass ratio of 1∶2 between the graphene oxide and bean dregs exhibited the maximum specific capacitance of 201.9 F/g at a current density of 1 A/g.The specific capacitance of 1 G2 BD-HC was much higher than that for carbon materials prepared from pure bean dregs and pure graphene oxide,which were 78.0 and 93.0 F/g at a current density of1 A/g,respectively.
引文
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[2] Zhang X,Zhang H,Li C,et al.Rencent advances in porous grapheme materials for supercapacitor applications[J].Rsc Advances,2014,86(4):45862-45884.
[3] Cheng Q,Tang J,Ma J,et al.Graphene and carbon nanotube composite electrodes for supercapacitors with ultra-high energy density[J].Physical Chemistry Chemical Physcis,2011,13(39):17615-24.
[4] Kholmanov I N,Magnuson C W,Piner R,et al.Optical,electrical,and electromechanical properties of hybrid graphene/carbon nanotube films[J].Advanced Materials,2015,27(19):3053-3059.
[5] You B,Wang L,Li Y,et al.Three dimensional N-doped graphene-CNT networks for supercapacitor[J].Chemical Communications,2013,49(44):5016-5018.
[6] Cui X,Lyu R,Sagar R U R,et al.Reduced graphene oxide/carbon nanotube hybrid film as high performance negative electrode for supercapacitor[J].Electrochimica Acta,2015,169:342-350.
[7] Li Y,Shang T X,Gao J M,et al.Nitrogen-doped activated carbon/graphene composites as high-performance supercapacitor electrodes[J].Rsc Advances,2017,7(31):19098-19105.
[8] Chen X,Oh W D,Hu Z T,et al.Enhancing sulfacetamide degradation by peroxymonosulfate activation with N-doped graphene produced through delicately-controlled nitrogen functionalization via tweaking thermal annealing processes[J].Applied Catalysis B:Environmental,2018,225:243–257.
[9] Wood K N,O'Hayre R,Pylypenko S.Recent progress on nitrogen/carbon structures designed for use in energy and sustainability applications[J].Energy&Environmental Science,2014,7(4):1212-1249.
[10] Sun L,Wang L,Tian C,et al.Nitrogen-doped graphene with high nitrogen level via a one-step hydrothermal reaction of graphene oxide with urea for superior capacitive energy storage[J].Rsc Advances,2012,2(10):4498-4506.
[11] Zhao H,Hui K S,Hui K N.Synthesis of nitrogendoped multilayer graphene from milk powder with melamine and their application to fuel cells[J].Carbon,2014,76(9):1-9.
[12] Ru H,Xiang K,Zhou W,et al.Bean-dreg-derived carbon materials used as superior anode material for lithium-ion batteries[J].Electrochimica Acta,2016,222:551-560.
[13] Xiang Kaixiong,Wang Xianyou,Chen Han,et al.Effect of pore structure of the bean dregs activated carbon on the performance of Li-S batteries[J].Journal of Functional Materials,2017,48(8):97-101(in Chinese).向楷雄,王先友,陈晗,等.豆渣活性炭孔结构对锂硫电池性能的影响[J].功能材料,2017,48(8):97-101.
[14] Jung H J,Park K H,Chan K,et al.Highly porous carbon sorbents prepared from bean dregs for electric double-layer supercapacitor[J].Transactions on Electrical and Electronic Materials,2018,19(3):1-6.
[15] Teng Y,Liu K,Liu R,et al.A novel copper nanoparticles/bean dregs-based activated carbon composite as pseudocapacitors[J].Materials Research Bulletin,2017,89:33-44.
[16] Zhou Baotian.Preparation of nitrogen-containing carbon materials from pyrolyse okara and its application in electrocatalysis[D].LanZhou:Northwest Normal University,2014(in Chinese).周田宝.豆渣热解制备含氮碳材料及其在电催化中的应用[D].兰州:西北师范大学,2014.
[17] Zhang Fuqin.Study on graphitization degree of C/C composites for aviation brake[D].Changsha:Central South University,2002(in Chinese).张福勤.航空刹车用C/C复合材料石墨化度的研究[D].长沙:中南大学,2002.
[18] Sun Li,Ruan Xinjin,Zhang Suipeng,et al.The netcarbon nanotubessupported nitrogen-doped porouscarbon composite by hydrothermal-assembly method fortheir energy storage properties[J].Journal of Functional Materials,2017,48(5):5017-5022(in Chinese).孙立,阮曦金,张岁鹏,等.水热组装法制备碳纳米管网状支撑氮掺杂多孔碳材料及其储能特性研究[J].功能材料,2017,48(5):5017-5022.
[19] Guo Kunkun,Chen Peng,Li Zhu,et al.Study on preparation and electrochemical performance of nitrogen-doped porous carbon[J].Journal of Hunan University(Natural sciences),2018,45(6):78-84(in Chinese).郭坤琨,陈鹏,李柱.氮掺杂多孔碳的制备及其电化学研究[J].湖南大学学报,2018,45(6):78-64.