高容量聚苯胺电极材料的结构化生长及电化学性质研究
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摘要
目的通过化学氧化聚合法在高导电性碳布基底上生长聚苯胺纳米阵列材料(C-clothPANI),并通过三电极体系研究其电化学性质。方法在酸性介质中,以碳布为高导电性生长基底、过硫酸铵为氧化剂使苯胺单体发生聚合制备高容量结构化生长的聚苯胺电极材料。用拉曼光谱、X射线衍射和场发射扫描电镜等分析方法对其结构及微观形貌进行表征。在三电极体系中,以饱和甘汞电极作为参比电极、金属铂电极作为辅助电极、负载聚苯胺纳米材料的碳布作为工作电极,在1mol/L H2SO4电解液中进行循环伏安测试、恒电流充放测试。结果 C-cloth-PANI电极材料呈现纳米阵列结构,排列整齐。在电流密度为1A/g时,其质量比电容为595F/g。当电流密度增大至20A/g时,其倍率性能高达86.4%,优于PANI纳米电极材料(365F/g,75.3%)。结论将聚苯胺直接生长在高导电性基底上,有利于优化电极结构、提高电荷传输速度、增加活性材料利用效率。
Purposes—To prepare polyaniline electrode material supported on highly-conductive carbon cloth(C-cloth-PANI)by chemical oxidative polymerization,and to study the electrochemical properties with the three-electrode system.Methods—With highly-conductive carbon cloth as the substrate for polyaniline to grow and(NH4)2S2O8as oxygenant,the C-cloth-PANI was prepared by in-situ oxidative polymerization of aniline monomers under an acid condition.Raman spectroscopy,X-ray diffraction(XRD)and field emission scanning electron microscopy(FESEM)were used to characterize the structure and morphology.In the three electrode system,with a saturated calomel electrode as reference electrode,metal platinum electrode as auxiliary electrode and C-clothPANI as working electrode,the electrochemical measurements were performed by cyclic voltammetry and galvanostatic charge and discharge tests in 1mol/L H2SO4 electrolyte.Result—The C-clothPANI electrode material exhibits the nano-array structure and is arranged neatly.At a current density of 1A/g,the mass specific capacitance was 595F/g.When the current density was increased to 20A/g,its rate performance was as high as 86.4%,which is better than PANI nano-electrode material(365F/g,75.3%).Conclusion—Making polyaniline grow on highly-conductive carbon cloth substrate,which is beneficial to optimize electrode structure,not only improves charge transfer speed but also increases the utilization efficiency of active materials.
Purposes—To prepare polyaniline electrode material supported on highly-conductive carbon cloth(C-cloth-PANI)by chemical oxidative polymerization,and to study the electrochemical properties with the three-electrode system.Methods—With highly-conductive carbon cloth as the substrate for polyaniline to grow and(NH4)2S2O8as oxygenant,the C-cloth-PANI was prepared by in-situ oxidative polymerization of aniline monomers under an acid condition.Raman spectroscopy,X-ray diffraction(XRD)and field emission scanning electron microscopy(FESEM)were used to characterize the structure and morphology.In the three electrode system,with a saturated calomel electrode as reference electrode,metal platinum electrode as auxiliary electrode and C-clothPANI as working electrode,the electrochemical measurements were performed by cyclic voltammetry and galvanostatic charge and discharge tests in 1mol/L H2SO4 electrolyte.Result—The C-clothPANI electrode material exhibits the nano-array structure and is arranged neatly.At a current density of 1A/g,the mass specific capacitance was 595F/g.When the current density was increased to 20A/g,its rate performance was as high as 86.4%,which is better than PANI nano-electrode material(365F/g,75.3%).Conclusion—Making polyaniline grow on highly-conductive carbon cloth substrate,which is beneficial to optimize electrode structure,not only improves charge transfer speed but also increases the utilization efficiency of active materials.
引文
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[2]WANG K,WU H,MENG Y,et al.Conducting polymer nanowire arrays for high performance supercapacitors[J].Small,2014,10(1):14-31.
[3] PARK H-W,KIM T,HUH J,et al.Anisotropic growth control of polyaniline nanostructures and their morphology-dependent electrochemical characteristics[J]. ACS Nano, 2014, 6(9):7624-7633.
[4] WANG K,HUANG J,WEI Z.Conducting polyaniline nanowire arrays for high performance supercapacitors[J].Journal of Physical Chemistry C,2010,114(17):8062-8067.
[5] WANG G,ZHANG L,ZHANG J.A review of electrode materials for electrochemical supercapacitors[J].Chemistry Society Reviews,2012,43(18):797-828.
[6] GROVER S,GOEL S,SAHU V,et al.Asymmetric supercapacitive characteristics of PANI embedded holey graphene nanoribbons[J].ACS Sustainable Chemistry Engineering, 2015, 3(7),1460-1469.
[7]WU W,LI Y,ZHAO G,et al.Aldehyde-poly(ethylene glycol)modified graphene oxide/conducting polymers composite as high-performance electrochemical supercapacitors[J].Journal of Materials Chemistry A,2014,2(42):18058-18069.
[8]PENG Y Y,LIU Y M,CHANG J K,et al.A facile approach to produce holey graphene and its application in supercapacitors[J].Carbon,2015,81(1):347-356.
[9] BAI Y,YANG X,HE Y,et al.Formation process of holey graphene and its assembled binder-free film electrode with high volumetric capacitance[J].Electrochimica Acta,2016,187:543-551.
[10] WANG G,WANG H,LU X,et al.Solid-state supercapacitor based on activated carbon cloths exhibits excellent rate capability[J].Advanced Materials,2014,26(17):2676-2682.
[11]张家奎.聚苯胺与石墨烯基复合材料的制备研究[D].天津:天津大学,2012.
[12] FAN W,ZHANG C,WENG W T,et al.Graphene-wrapped polyaniline hollow spheres as novel hybrid electrode materials for supercapacitor applications[J].ACS Applied Materials&Interfaces,2013,5(8):3382-3391.
[13] REN L,ZHANG G,LEI J,et al.Novel layered polyaniline-poly(hydroquinone)/graphene film as supercapacitor electrode with enhanced rate performance and cycling stability[J].Journal of Colloid Interface Science,2017,512:300-307.
[14]WANG K,ZHAO P,ZHOU X,et al.Flexible supercapacitors based on cloth-supported electrodes of conducting polymer nanowire array/SWCNT composites[J].Journal of Materials Chemistry,2011,21(41):16373-16378.
[15] MENG Y,WANG K,ZHANG Y,et al.Hierarchical porous graphene/polyaniline composite film with superior rate performance for flexible supercapacitors[J].Advanced Materials,2013,25(48):6985-6990.
[16] REN L,ZHANG G,YAN Z,et al.Three-dimensional tubular MoS2/PANI hybrid electrode for high rate performance supercapacitor[J].ACS Applied Materials&Interfaces,2015,7(51):28294-28302.
[17]任莉君,张改妮,王艳,等.聚苯胺纳米球电极材料的制备及其电容性质[J].功能材料,2017,12(48):12200-12204.
[18] XU Y,TAO Y,ZHENG Xu,et al.A metalfree supercapacitor electrode material with a record high volumetric capacitance over 800F·cm–3[J].Advanced Materials,2015,27(48):8082-8087.
[19] REN L,ZHANG G,WANG J,et al.Adsorption-template preparation of polyanilines with different morphologies and their capacitance[J].Electrochimica Acta,2014,145(145):99-108.
[20] ZHANG X,MA L,GAN M,et al.Controllable constructing of hollow MoS2/PANI core/shell microsphere for energy storage[J].Applied Surface Science,2017,DOI:10.1016/j.apsusc.2017.10.010.