三维多级孔石墨烯/聚苯胺复合材料的制备及电化学性能
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摘要
采用水热法合成聚糠醇(PFA),探究了表面活性剂聚乙烯吡咯烷酮(PVP)添加量和反应时间对PFA微观形貌的影响。将改进Hummers法制备的氧化石墨烯(GO)对PFA、泡沫Ni进行包覆,探讨了PFA模板与GO不同质量比的包覆效果。去模板后成功构筑三维大孔石墨烯(3DrGO),3DrGO再经KOH活化获得三维多级孔石墨烯(3DPrGO),3DPrGO经与聚苯胺(PANI)原位复合获得3DPrGO/PANI复合材料。采用XRD、SEM、TEM、FTIR、XPS和比表面(BET)分析法对材料的物相组成、微观结构、形貌、比表面和孔径进行表征,采用循环伏安、恒流充放电、电化学阻抗谱分析了3DPrGO/PANI复合材料的电化学性能。结果表明:通过控制糠醇、PVP及水的比例,在180℃水热反应24h成功制备了球径在500nm左右的PFA微球。在PFA与GO质量比为1∶1时包覆效果最佳。450℃热处理6h成功去除PFA模板并形成400～600nm左右的大孔,经KOH活化后,在3DPrGO上形成介孔结构。3DPrGO/PANI复合材料在0.5A/g电流密度下比电容为433F/g,在1A/g下1 000次循环充放电之后,3DPrGO/PANI复合材料的比电容保留率为75%,高于纯PANI的69%。
Poly(furfuryl alcohol)(PFA)was synthesized by the hydrothermal method.The effect of surfactant polyvinylpyrrolidone(PVP)amount and hydrothermal duration on the micromorphology of PFA was investigated.PFA and Ni foam were coated with graphene oxide(GO)prepared by the modified Hummers method,and the coating effects of different mass ratios of PFA∶GO were investigated.3 D macroporous graphene(3 DrGO)was successfully built through removing PFA and Ni foam templates.3 Dhierarchical porous graphene(3 DPrGO)was constructed on 3 DrGO by KOH activation.3 DPrGO/PANI was synthesized by in-situ composite.The phase composition,microstructure and morphology were analyzed by XRD,SEM,TEM,FTIR,XPS and Brunner-Emmet-Teller(BET)measurements.The electrochemical performance of the composites was analyzed by cyclic voltammetry,galvanostatic charge-discharge and electrochemical impedance spectroscopy.The results show that PFA microspheres with a diameter of about 500 nm are successfully synthesized by controlling the ratio of furfuryl alcohol,PVP and water at 180℃for 24 h.The coating effect is the best at mass ratio of PFA∶GO=1∶1.The PFA templates are successfully removed by heat treatment at 450℃for 6 hand pore sizes of 400-600 nm are formed.The mesopores are formed on the 3 DrGO after KOH activation.The specific capacitance of 3 DPrGO/PANI composites is 433 F/g at 0.5 A/g,and retains 75% after 1 000 cycling at 1 A/g,which is higher than that of pure PANI(69%).
Poly(furfuryl alcohol)(PFA)was synthesized by the hydrothermal method.The effect of surfactant polyvinylpyrrolidone(PVP)amount and hydrothermal duration on the micromorphology of PFA was investigated.PFA and Ni foam were coated with graphene oxide(GO)prepared by the modified Hummers method,and the coating effects of different mass ratios of PFA∶GO were investigated.3 D macroporous graphene(3 DrGO)was successfully built through removing PFA and Ni foam templates.3 Dhierarchical porous graphene(3 DPrGO)was constructed on 3 DrGO by KOH activation.3 DPrGO/PANI was synthesized by in-situ composite.The phase composition,microstructure and morphology were analyzed by XRD,SEM,TEM,FTIR,XPS and Brunner-Emmet-Teller(BET)measurements.The electrochemical performance of the composites was analyzed by cyclic voltammetry,galvanostatic charge-discharge and electrochemical impedance spectroscopy.The results show that PFA microspheres with a diameter of about 500 nm are successfully synthesized by controlling the ratio of furfuryl alcohol,PVP and water at 180℃for 24 h.The coating effect is the best at mass ratio of PFA∶GO=1∶1.The PFA templates are successfully removed by heat treatment at 450℃for 6 hand pore sizes of 400-600 nm are formed.The mesopores are formed on the 3 DrGO after KOH activation.The specific capacitance of 3 DPrGO/PANI composites is 433 F/g at 0.5 A/g,and retains 75% after 1 000 cycling at 1 A/g,which is higher than that of pure PANI(69%).
引文
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[2]方寅.纳米尺寸介孔碳材料的合成、性质与应用[D].上海:复旦大学,2013.FANG Y.Synthesis,properties and application of meso pore carbon with nano size[D].Shanghai:Fudan University,2013(in Chinese).
[3]HAN S,WU D,LI S,et al.Porous graphene materials for advanced electrochemical energy storage and conversion devices[J].Advanced Materials,2014,26(6):849-864.
[4]NOVOSELOV K S,GEIM A K,MOROZOV S V,et al.Electric field effect in atomically thin carbon films[J].Science,2004,306(5696):666-669.
[5]CHEN D,FENG H B,LI J H.Graphene oxide preparation functionalization and electrochemical applications[J].Chemical Reviews,2012,112(11):6027-6053.
[6]任芳,朱光明,任鹏刚.纳米石墨烯复合材料的制备及应用研究进展[J].复合材料学报,2014,31(2):263-272.REN F,ZHU G M,REN P G.The latest advances in preparation and application of nano graphene composites[J].Acta Materiae Compositae Sinica,2014,31(2):263-272(in Chinese).
[7]NAIR R R,WU H A,JAYARAM P N,et al.Unimpeded permeation of water through helium-leak-tight graphenebased membranes[J].Science,2012,335(6067):442-444.
[8]YANG T S,LIN H,ZHENG X R,et al.Tailoring pores in graphene-based materials:From generation to applications[J].Journal of Materials Chemistry A,2017,5(32):16537-16558.
[9]徐如人,庞文琴,霍启升,等.分子筛与多孔材料[M].北京:科学出版社,2015.XU R R,PANG W Q,HUO Q S,et al.Molecular sieves and porous materials[M].Beijing:Science Press,2015(in Chinese).
[10]吴小辉,洪孝挺,南俊民,等.模板法合成多孔炭材料的研究现状[J].材料导报,2012,26(7):61-65.WU X H,HONG X T,NAN J M,et al.Research status of synthesizing porous carbon materials by template method[J].Materials Review,2012,26(7):61-65(in Chinese).
[11]蔡彬,胡炜,杜宝吉,等.模板法及其在纳米材料制备领域的应用研究进展[J].材料导报,2010,24(15):107-112.CAI B,HU W,DU B J,et al.Template method and its application in preparation of nanomaterials[J].Materials Review,2010,24(15):107-112(in Chinese).
[12]PALANIAPPAN S,DEVI S L.Novel chemically synthesized polyaniline electrodes containing a fluoroboric acid dopant for supercapacitors[J].Journal of Applied Polymer Science,2010,107(3):1887-1892.
[13]袁冰清,郁黎明,盛雷梅,等.石墨烯/聚苯胺复合材料的电磁屏蔽性能[J].复合材料学报,2013,30(1):22-26.YUAN B Q,YU L M,SHENG L M,et al.Graphene sheets/polyaniline composite for electromagnetic interference shielding[J].Acta Materiae Compositae Sinica,2013,30(1):22-26(in Chinese).
[14]ZHANG Q Q,LI Y,FENG Y Y,et al.Electropolymerization of graphene oxide/polyaniline composite for high-performance supercapacitor[J].Electrochimica Acta,2013,90(5):95-100.
[15]范艳煌,邹正光,龙飞,等.以氧化石墨烯为氧化介质制备石墨烯/聚苯胺导电复合材料[J].复合材料学报,2013,30(1):27-31.FAN Y H,ZOU Z G,LONG F,et al.Preparation of graphene polyanilline conducting composite by graphene oxide for oxidant[J].Acta Materiae Compositae Sinica,2013,30(1):27-31(in Chinese).
[16]ZHANG K,ZHANG L L,ZHAO X S,et al.Graphene/polyaniline nanofiber composites as supercapacitor electrodes[J].Chemistry of Materials,2010,22(4):1392-1401.
[17]YANG B,YANG H Y,YING H,et al.A novel electrochemical DNA biosensor based on graphene and polyaniline nanowires[J].Electrochimica Acta,2011,56(6):2676-2681.
[18]QIU H,HAN X,QIU F,et al.Facile route to covalentlyjointed graphene/polyaniline composite and it’s enhanced electrochemical performances for supercapacitors[J].Applied Surface Science,2016,376:261-268.
[19]LIU Y,MA Y,GUANG S Y,et al.Polyaniline-graphene composites with a three-dimentional array-based nanostructure for high performance supercapacitors[J].Carbon,2015,83:79-89.
[20]LU X,LI L,SONG B,et al.Mechanistic investigation of the graphene functionalization using p-phenylenediamine and its application for supercapacitors[J].Nano Energy,2015,17(1):160-170.
[21]WU S L,CHEN G X,KIM N Y,et al.Creating pores on graphene platelets by low-temperature KOH activation for enhanced electrochemical performance[J].Small,2016,12(17):2376-2384.
[22]翟赟璞.有序介孔聚糠醇的组装及有序介孔碳材料的合成与功能化修饰[D].上海:复旦大学,2009.ZHAI Y P.Assembly of ordered mesoporous poly furfuryl alcohol and synthesis and functional modification of ordered mesoporous carbon materials[D].Shanghai:Fudan University,2009(in Chinese).
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[24]HU H,LIU S W,HANIF M,et al.Three-dimentional cross-lingked carbon network wrapped with ordered polyaniline nanowires for high-performance pseudo-supercapacitors[J].Journal of Power Sources,2014,268(3):451-458.