一步法制备氧化石墨烯/聚苯胺/Au复合材料及电化学性能
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摘要
以改进的Hummers法制备的氧化石墨烯为基底,以氯金酸为氧化剂和金源,原位聚合苯胺单体,一步制得氧化石墨烯/聚苯胺/金(GO/PANI/Au)三元复合材料。形貌和成分分析结果表明,氯金酸成功地将苯胺氧化成聚苯胺,并被还原生成金纳米颗粒。电化学性能测试结果表明,随着氧化剂用量的增加,三元复合材料的比电容呈现先增大后减小的趋势,当氧化剂加入量为0.03mmol时,所制备的三元复合材料比电容最大,在1A/g电流密度、1mol/L H2SO4电解液中比容量达327F/g,在15A/g电流密度下容量保持率也高达81%。
The graphene oxide/polyaniline/gold(GO/PANI/Au)ternary composites were prepared successfully by one step method.The graphene oxide prepared by the modified Hummers method was used as the substrate,and the aniline monomer was polymerized in situ by using chloroauric acid as the oxidant and the gold source.The morphology and composition analysis showed that chloroauric acid successfully oxidized aniline to polyaniline and was reduced to gold nanoparticles.The electrochemical performance test showed that the specific capacitance of the ternary composites increased first and then decreased with the increase of the amount of oxidant.When the oxidant was added in an amount of 0.03 mmol,the prepared ternary composite had the largest specific capacitance.The specific capacity is 327 F/g at a current density of 1 A/g in 1 mol/L H2 SO4 electrolyte.When the current density reached at 15 A/g,the capacity retention rate was still as high as 81%compared with initial current density.
The graphene oxide/polyaniline/gold(GO/PANI/Au)ternary composites were prepared successfully by one step method.The graphene oxide prepared by the modified Hummers method was used as the substrate,and the aniline monomer was polymerized in situ by using chloroauric acid as the oxidant and the gold source.The morphology and composition analysis showed that chloroauric acid successfully oxidized aniline to polyaniline and was reduced to gold nanoparticles.The electrochemical performance test showed that the specific capacitance of the ternary composites increased first and then decreased with the increase of the amount of oxidant.When the oxidant was added in an amount of 0.03 mmol,the prepared ternary composite had the largest specific capacitance.The specific capacity is 327 F/g at a current density of 1 A/g in 1 mol/L H2 SO4 electrolyte.When the current density reached at 15 A/g,the capacity retention rate was still as high as 81%compared with initial current density.
引文
[1] Futaba D N,Hata K,Yamada T,et al.Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes.[J].Nature Materials,2006,5(12):987-994.
[2] Teymourfar R,Asaei B,Iman-Eini H,et al.Stationary super-capacitor energy storage system to save regenerative braking energy in a metro line[J].Energy Conversion&Management,2012,56(2):206-214.
[3] Deng F,Qiu H,Chen J,et al.Wearable thermoelectric power generators combined with flexible super capacitor for low-power human diagnosis devices[J].IEEE Transactions on Industrial Electronics,2017,PP(99):1-1.
[4] Huang S C,Huang S M,Ng H,et al.Polyaniline capacitors[J].Synthetic Metals,1993,57(1):4047-4052.
[5] Feng L W,Zhen Y Y,Liu X G,et al.Preparation and electrochemical performance of a polyaniline-carbon microsphere hybrid as a supercapacitor electrode[J].New Carbon Materials,2016,31(6):594-599.
[6] Wen L,Li K,Liu J,et al.Graphene/polyaniline@carbon cloth composite as a high-performance flexible supercapacitor electrode prepared by a one-step electrochemical co-deposition method[J].Rsc Advances,2017,7(13):7688-7693.
[7] Yu T,Zhu P,Xiong Y,et al.Synthesis of microspherical polyaniline/graphene composites and their application in supercapacitors[J].Electrochimica Acta,2016,222:12-19.
[8] Xu W,Mu B,Zhang W,et al.Facile hydrothermal synthesis of tubular kapok fiber/MnO2composites and application in supercapacitors[J].Rsc Advances,2015,5(79):64065-64075.
[9] Zhu Y P,Liu Y L,Ren T Z,et al.Hollow manganese phosphonate microspheres with hierarchical porosity for efficient adsorption and separation[J].Nanoscale,2014,6(12):6627-6636.
[10] Qu B,Hu L,Chen Y,et al.Rational design of Au-NiO hierarchical structures with enhanced rate performance for supercapacitors[J].Journal of Materials Chemistry A,2013,1(24):7023-7026.
[11] Kim S I,Thiyagarajan P,Jang J H.Great improvement in pseudocapacitor properties of nickel hydroxide via simple gold deposition.[J].Nanoscale,2014,6(20):11646-11652.
[12] UrbanovV,Bakandritsos A,Jakubec P,et al.A facile graphene oxide based sensor for electrochemical detection of neonicotinoids.[J].Biosensors&Bioelectronics,2016,89(Pt 1):532-537.
[13] Dai H,Wang N,Wang D,et al.An electrochemical sensor based on phytic acid functionalized polypyrrole/graphene oxide nanocomposites for simultaneous determination of Cd(Ⅱ)and Pb(Ⅱ)[J].Chemical Engineering Journal,2016,299:150-155.
[14] Dan X,Yingxia M A,Yongxin R,et al.Preparation and characterization of amino-functionalized magnetic graphite nanosheet nanocomposites[J].Chemical Journal of Chinese Universities,2016,37(11):1947-1952(in Chinese).邢丹,马应霞,阮永欣,等.胺基改性磁性纳米石墨片复合材料的制备与表征[J].高等学校化学学报,2016,37(11):1947-1952.
[15] Zhan Y,Wan X,Long Z,et al.Two step hydrothermal synthesis of flowerbud-like magnetite/graphene oxide hybrid with high-performance microwave absorption[J].Russian Journal of Applied Chemistry,2016,89(2):297-303.
[16] Sun J,Bi H.Pickering emulsion fabrication and enhanced supercapacity of graphene oxide-covered polyaniline nanoparticles[J].Materials Letters,2012,81(4):48-51.
[17] Liu L,Yang J,Jiang Y,et al.The structure characteristic and electrochemical performance of graphene/polyaniline composites[J].Synthetic Metals,2013,170(1):57-62.
[18] Tan Yongtao,Kong Lingbin,Kang Long,et al.Construction of nano-Au@PANI yolk-shell hollow structure electrode material and its electrochemical performance[J].Materials Review,2018,32(1):47-50(in Chinese).谭永涛,孔令斌,康龙,等.Nano-Au@PANI蛋黄空心结构电极材料的构筑及超级电容性能[J].材料导报,2018,32(1):47-50.
[19] Shayeh J S,Ehsani A,Ganjali M R,et al.Conductive polymer/reduced graphene oxide/Au nano particles as efficient composite materials in electrochemical supercapacitors[J].Applied Surface Science,2015,353:594-599.
[20] Shen J,Hu Y,Shi M,et al.Fast and facile preparation of graphene oxide and reduced graphene oxide nanoplatelets[J].Chemistry of Materials,2009,21(15):3514-3520.
[21] Han Xiao,Wang You,Liu Shujuan,et al.Research of PpPD/GO/Au nanocomposite:synthesis and supercapacitor properties[J].Journal of Functional Materials,2011,42(s4):744-747(in Chinese).韩啸,王铀,刘淑娟,等.聚苯胺/石墨烯/金复合材料的制备及超电容性能研究[J].功能材料,2011,42(s4):744-747.
[22] Veerapandian M,Lee M H,Krishnamoorthy K,et al.Synthesis,characterization and electrochemical properties of functionalized graphene oxide[J].Carbon,2012,50(11):4228-4238.
[23] Saha S,Mitra M,Sarkar A,et al.Lithium assisted enhanced hydrogenation of reduced graphene oxide-PANI nanocomposite at room temperature[J].Diamond&Related Materials,2018,84:103-111.
[24] Hou J,Zhang L,Qiu H,et al.Fabrication and microwave absorption performances of hollow-structure Fe3O4/PANI microspheres[J].Journal of Materials Science Materials in Electronics,2017,28(13):9279-9288.
[25] Mu B,Zhang W,Wang A.Template synthesis of graphene/polyaniline hybrid hollow microspheres as electrode materials for high-performance supercapacitor[J].Journal of Nanoparticle Research,2014,16(6):1-12.
[26] Chen P C,Shen G,Shi Y,et al.Preparation and characterization of flexible asymmetric supercapacitors based on transition-metal-oxide nanowire/single-walled carbon nanotube hybrid thin-film electrodes.[J].ACS Nano,2010,4(8):4403-4412.
[27] Tan Y,Liu Y,Kong L,et al.In situ doping of PANI nanocomposites by gold nanoparticles for high-performance electrochemical energy storage[J].Journal of Applied Polymer Science,2017,134(38):45309-45318.
[28] Su Haibo,Zhu Pengli,Li Tingxi,et al.Preparation and study of the paper fiber-based flexible supercapacitors electrode with reduced graphene oxide and polyaniline hybrid materials[J].Journal of Integration Technology,2017,6(1):16-23(in Chinese).苏海波,朱朋莉,李廷希,等.纸纤维基柔性还原氧化石墨烯、聚苯胺超级电容器复合电极材料的制备与性能研究[J].集成技术,2017,6(1):16-23.
[29] Xu W,Mu B,Wang A.From adsorbents to electrode materials:facile hydrothermal synthesis of montmorillonite/polyaniline/metal oxide(hydroxide)composites[J].New Journal of Chemistry,2016,40(3):2687-2695.
[30] Luo Y,Liu L,Qiao W,et al.Facile crystal-structurecontrolled synthesis of iron oxides for adsorbents and anode materials of lithium batteries[J].Materials Chemistry&Physics,2016,170(49):239-245.
[31] Zhang W,Mu B,Wang A.Preparation of manganese dioxide/multiwalled carbon nanotubes hybrid hollow microspheres via layer-by-layer assembly for supercapacitor[J].Journal of Materials Science,2013,48(21):7581-7586.
[2] Teymourfar R,Asaei B,Iman-Eini H,et al.Stationary super-capacitor energy storage system to save regenerative braking energy in a metro line[J].Energy Conversion&Management,2012,56(2):206-214.
[3] Deng F,Qiu H,Chen J,et al.Wearable thermoelectric power generators combined with flexible super capacitor for low-power human diagnosis devices[J].IEEE Transactions on Industrial Electronics,2017,PP(99):1-1.
[4] Huang S C,Huang S M,Ng H,et al.Polyaniline capacitors[J].Synthetic Metals,1993,57(1):4047-4052.
[5] Feng L W,Zhen Y Y,Liu X G,et al.Preparation and electrochemical performance of a polyaniline-carbon microsphere hybrid as a supercapacitor electrode[J].New Carbon Materials,2016,31(6):594-599.
[6] Wen L,Li K,Liu J,et al.Graphene/polyaniline@carbon cloth composite as a high-performance flexible supercapacitor electrode prepared by a one-step electrochemical co-deposition method[J].Rsc Advances,2017,7(13):7688-7693.
[7] Yu T,Zhu P,Xiong Y,et al.Synthesis of microspherical polyaniline/graphene composites and their application in supercapacitors[J].Electrochimica Acta,2016,222:12-19.
[8] Xu W,Mu B,Zhang W,et al.Facile hydrothermal synthesis of tubular kapok fiber/MnO2composites and application in supercapacitors[J].Rsc Advances,2015,5(79):64065-64075.
[9] Zhu Y P,Liu Y L,Ren T Z,et al.Hollow manganese phosphonate microspheres with hierarchical porosity for efficient adsorption and separation[J].Nanoscale,2014,6(12):6627-6636.
[10] Qu B,Hu L,Chen Y,et al.Rational design of Au-NiO hierarchical structures with enhanced rate performance for supercapacitors[J].Journal of Materials Chemistry A,2013,1(24):7023-7026.
[11] Kim S I,Thiyagarajan P,Jang J H.Great improvement in pseudocapacitor properties of nickel hydroxide via simple gold deposition.[J].Nanoscale,2014,6(20):11646-11652.
[12] UrbanovV,Bakandritsos A,Jakubec P,et al.A facile graphene oxide based sensor for electrochemical detection of neonicotinoids.[J].Biosensors&Bioelectronics,2016,89(Pt 1):532-537.
[13] Dai H,Wang N,Wang D,et al.An electrochemical sensor based on phytic acid functionalized polypyrrole/graphene oxide nanocomposites for simultaneous determination of Cd(Ⅱ)and Pb(Ⅱ)[J].Chemical Engineering Journal,2016,299:150-155.
[14] Dan X,Yingxia M A,Yongxin R,et al.Preparation and characterization of amino-functionalized magnetic graphite nanosheet nanocomposites[J].Chemical Journal of Chinese Universities,2016,37(11):1947-1952(in Chinese).邢丹,马应霞,阮永欣,等.胺基改性磁性纳米石墨片复合材料的制备与表征[J].高等学校化学学报,2016,37(11):1947-1952.
[15] Zhan Y,Wan X,Long Z,et al.Two step hydrothermal synthesis of flowerbud-like magnetite/graphene oxide hybrid with high-performance microwave absorption[J].Russian Journal of Applied Chemistry,2016,89(2):297-303.
[16] Sun J,Bi H.Pickering emulsion fabrication and enhanced supercapacity of graphene oxide-covered polyaniline nanoparticles[J].Materials Letters,2012,81(4):48-51.
[17] Liu L,Yang J,Jiang Y,et al.The structure characteristic and electrochemical performance of graphene/polyaniline composites[J].Synthetic Metals,2013,170(1):57-62.
[18] Tan Yongtao,Kong Lingbin,Kang Long,et al.Construction of nano-Au@PANI yolk-shell hollow structure electrode material and its electrochemical performance[J].Materials Review,2018,32(1):47-50(in Chinese).谭永涛,孔令斌,康龙,等.Nano-Au@PANI蛋黄空心结构电极材料的构筑及超级电容性能[J].材料导报,2018,32(1):47-50.
[19] Shayeh J S,Ehsani A,Ganjali M R,et al.Conductive polymer/reduced graphene oxide/Au nano particles as efficient composite materials in electrochemical supercapacitors[J].Applied Surface Science,2015,353:594-599.
[20] Shen J,Hu Y,Shi M,et al.Fast and facile preparation of graphene oxide and reduced graphene oxide nanoplatelets[J].Chemistry of Materials,2009,21(15):3514-3520.
[21] Han Xiao,Wang You,Liu Shujuan,et al.Research of PpPD/GO/Au nanocomposite:synthesis and supercapacitor properties[J].Journal of Functional Materials,2011,42(s4):744-747(in Chinese).韩啸,王铀,刘淑娟,等.聚苯胺/石墨烯/金复合材料的制备及超电容性能研究[J].功能材料,2011,42(s4):744-747.
[22] Veerapandian M,Lee M H,Krishnamoorthy K,et al.Synthesis,characterization and electrochemical properties of functionalized graphene oxide[J].Carbon,2012,50(11):4228-4238.
[23] Saha S,Mitra M,Sarkar A,et al.Lithium assisted enhanced hydrogenation of reduced graphene oxide-PANI nanocomposite at room temperature[J].Diamond&Related Materials,2018,84:103-111.
[24] Hou J,Zhang L,Qiu H,et al.Fabrication and microwave absorption performances of hollow-structure Fe3O4/PANI microspheres[J].Journal of Materials Science Materials in Electronics,2017,28(13):9279-9288.
[25] Mu B,Zhang W,Wang A.Template synthesis of graphene/polyaniline hybrid hollow microspheres as electrode materials for high-performance supercapacitor[J].Journal of Nanoparticle Research,2014,16(6):1-12.
[26] Chen P C,Shen G,Shi Y,et al.Preparation and characterization of flexible asymmetric supercapacitors based on transition-metal-oxide nanowire/single-walled carbon nanotube hybrid thin-film electrodes.[J].ACS Nano,2010,4(8):4403-4412.
[27] Tan Y,Liu Y,Kong L,et al.In situ doping of PANI nanocomposites by gold nanoparticles for high-performance electrochemical energy storage[J].Journal of Applied Polymer Science,2017,134(38):45309-45318.
[28] Su Haibo,Zhu Pengli,Li Tingxi,et al.Preparation and study of the paper fiber-based flexible supercapacitors electrode with reduced graphene oxide and polyaniline hybrid materials[J].Journal of Integration Technology,2017,6(1):16-23(in Chinese).苏海波,朱朋莉,李廷希,等.纸纤维基柔性还原氧化石墨烯、聚苯胺超级电容器复合电极材料的制备与性能研究[J].集成技术,2017,6(1):16-23.
[29] Xu W,Mu B,Wang A.From adsorbents to electrode materials:facile hydrothermal synthesis of montmorillonite/polyaniline/metal oxide(hydroxide)composites[J].New Journal of Chemistry,2016,40(3):2687-2695.
[30] Luo Y,Liu L,Qiao W,et al.Facile crystal-structurecontrolled synthesis of iron oxides for adsorbents and anode materials of lithium batteries[J].Materials Chemistry&Physics,2016,170(49):239-245.
[31] Zhang W,Mu B,Wang A.Preparation of manganese dioxide/multiwalled carbon nanotubes hybrid hollow microspheres via layer-by-layer assembly for supercapacitor[J].Journal of Materials Science,2013,48(21):7581-7586.