含氧纳米多孔碳球的制备及其在超级电容器中的应用
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摘要
开发具有规整纳米球状结构、高比表面积、高电化学活性且合成工艺简单的纳米多孔碳材料,对高储能设备至关重要。以β-环糊精为原料,采用高温水热、炭化以及氢氧化钾和碳酸钾活化制备纳米多孔碳球(NCSs),并对其进行硝酸和过硫酸铵表面氧化改性,系统研究了表面改性对多孔碳球电化学性能的影响。研究结果表明:NCSs呈规整球形结构,球直径200～300nm,比表面积为932.6m~2/g,经表面氧化改性后,球形结构并无发生较大的变化,但电化学性能有明显的提升,其中NCSs经过硫酸铵(APS)氧化改性后制得的NCSs-APS,在扫描速度为5mV/s条件下,比容量为214.1F/g,相比于NCSs(比容量为140.6F/g),比容量提升了52.3%。同时NCSs-APS具有良好的循环稳定性,经3000次循环,比容量保持率为91.4%。
Development of sample synthesis process for the fabrication of nanoporous carbon materials with well-nanospheric structure,large specific surface areas and high electrochemical performance is critical for the high electricity storage devices.Nanoporous carbon spheres(NCSs)were fabricated through a high-temperature hydrothermal carbonization,KOH/K_2 CO_3 activation process and subsequent surface-modified by a wet oxidation using nitric acid and ammonium peroxodisulfate with beta-cyclodextrin raw materials.The effect of surface modification on electrochemical performance was systematically investigated.Results shown that the NCSs was regularly spherical in the shape with demeter of 200～300 nm,and the specific surface was up to 932.6 m~2/g.After surface oxidation modification,there was no large charges in the spherical structure,but the electrochemical performance had obvious improvement.NCSs oxidized by ammonium peroxodisulfate(NCSs-APS)demonstrated excellent electrochemical performance which had gravimetric capacitance of 214.1 F/g at 5 mV/s and 52.3%improvement by NCSs(140.6 F/g).Meanwhile NCSs-APS exhibited favorite cycle stability,which retained over 91.4% of the specific capacitance after 3000 cycles.
Development of sample synthesis process for the fabrication of nanoporous carbon materials with well-nanospheric structure,large specific surface areas and high electrochemical performance is critical for the high electricity storage devices.Nanoporous carbon spheres(NCSs)were fabricated through a high-temperature hydrothermal carbonization,KOH/K_2 CO_3 activation process and subsequent surface-modified by a wet oxidation using nitric acid and ammonium peroxodisulfate with beta-cyclodextrin raw materials.The effect of surface modification on electrochemical performance was systematically investigated.Results shown that the NCSs was regularly spherical in the shape with demeter of 200～300 nm,and the specific surface was up to 932.6 m~2/g.After surface oxidation modification,there was no large charges in the spherical structure,but the electrochemical performance had obvious improvement.NCSs oxidized by ammonium peroxodisulfate(NCSs-APS)demonstrated excellent electrochemical performance which had gravimetric capacitance of 214.1 F/g at 5 mV/s and 52.3%improvement by NCSs(140.6 F/g).Meanwhile NCSs-APS exhibited favorite cycle stability,which retained over 91.4% of the specific capacitance after 3000 cycles.
引文
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[2]Lee J,Kim J,Hyeon T.Recent progress in the synthesis of porous carbon materials[J].Advanced Materials,2006,18(16):2073-2094.
[3]Liu J,Wickramaratne N P,Qiao S Z,et al.Molecular-based design and emerging applications of nanoporous carbon spheres[J].Nature Materials,2015,14(8):763-744.
[4]Tang J,Salunkhe R R,Liu J,et al.Thermal conversion of core-shell metal-organic frameworks:a new method for selectively functionalized nanoporous hybrid carbon[J].Journal of the American Chemical Society,2015,137(4):1572-1580.
[5]Lu A H,Hao G P,Sun Q,et al.Chemical synthesis of carbon materials with intriguing nanostructure and morphology[J].Macromolecular Chemistry and Physics,2012,213(10/11):1107-1131.
[6]Romero-Anaya A J,Ouzzine M,Lillo-Ródenas M A,et al.Spherical carbons:synthesis,characterization and activation processes[J].Carbon,2014,68:296-307.
[7]Choma J,Jamiola D,Augustynek K,et al.New opportunities in stober synthesis:preparation of microporous and mesoporous carbon spheres[J].Journal of Materials Chemistry,2012,22(25):12636-12642.
[8]Liu S,Cai Y,Zhao X,et al.Sulfur-doped nanoporous carbon spheres with ultrahigh specific surface area and high electrochemical activity for supercapacitor[J].Journal of Power Sources,2017,360:373-382.
[9]Fuertes A B,Valle-Vigón P,Sevilla M.One-step synthesis of silica@resorcinol-formaldehyde spheres and their application for the fabrication of polymer and carbon capsules[J].Chemical Communications,2012,48(49):6124-6126.
[10]Qiao Z A,Guo B,Binder A J,et al.Controlled synthesis of mesoporous carbon nanostructures via a“silica-assisted”strategy[J].Nano Letters,2012,13(1):207-212.
[11]Zhao W,Song C,Pehrsson P E.Water-soluble and optically pH-sensitive single-walled carbon nanotubes from surface modification[J].Journal of the American Chemical Society,2002,124(42):12418-12419.
[12]Lozano-Castello D,Cazorla-Amorós D,Linares-Solano A,et al.Influence of pore structure and surface chemistry on electric double layer capacitance in non-aqueous electrolyte[J].Carbon,2003,41(9):1765-1775.
[13]Tanaka S,Fujimoto H,Denayer J F M,et al.Surface modification of soft-templated ordered mesoporous carbon for electrochemical supercapacitors[J].Microporous and Mesoporous Materials,2015,217:141-149.
[14]Li H,Xi H,Zhu S,et al.Preparation,structural characterization,and electrochemical properties of chemically modified mesoporous carbon[J].Microporous and Mesoporous Materials,2006,96(1):357-362.
[15]Ren T Z,Liu L,Zhang Y,et al.Nitric acid oxidation of ordered mesoporous carbons for use in electrochemical supercapacitors[J].Journal of Solid State Electrochemistry,2013,17(8):2223-2233.
[16]Oda H,Yamashita A,Minoura S,et al.Modification of the oxygen-containing functional group on activated carbon fiber in electrodes of an electric double-layer capacitor[J].Journal of Power Sources,2006,158(2):1510-1516.
[17]Panichpakdee J,Pavasant P,Supaphol P.Electrospinning of asiaticoside/2-hydroxypropyl-β-cyclodextrin inclusion complex-loaded cellulose acetate fiber mats:release characteristics and potential for use as wound dressing[J].Polymer Korea,2014,38(3):338-350.
[18]Shen J,Xin X,Liu T,et al.Manipulation the properties of supramolecular hydrogels ofαyclodextrin/tyloxapol/carbonbased nanomaterials[J].Journal of Colloid and Interface Science,2016,468:78-85.
[19]Lyu Z,Xu D,Yang L,et al.Hierarchical carbon nanocages confining high-loading sulfur for high-rate lithium-sulfur batteries[J].Nano Energy,2015,12:657-665.
[20]Zhao Y,Liu M,Gan L,et al.Ultramicroporous carbon nanoparticles for the high-performance electrical double-layer capacitor electrode[J].Energy &Fuels,2014,28(2):1561-1568.
[21]Liu M,Qian J,Zhao Y,et al.Core-shell ultramicroporous@microporous carbon nanospheres as advanced supercapacitor electrodes[J].Journal of Materials Chemistry A,2015,3(21):11517-11526.
[22]Juan Y,Ke Q Q.Preparation of activated carbon by chemical activation under vacuum[J].Environmental Science &Technology,2009,43(9):3385-3390.
[23]Du Q,Zheng M,Zhang L,et al.Preparation of functionalized graphene sheets by a low-temperature thermal exfoliation approach and their electrochemical supercapacitive behaviors[J].Electrochimica Acta,2010,55(12):3897-3903.
[24]Li H,Xi H,Zhu S,et al.Preparation,structural characterization,and electrochemical properties of chemically modified mesoporous carbon[J].Microporous and Mesoporous Materials,2006,96(1):357-362.
[25]Wang J,Liu J,Chao D,et al.Self-assembly of honeycomb-like MoS2nanoarchitectures anchored into graphene foam for enhanced lithium-ion storage[J].Advanced Materials,2014,26(42):7162-7169.
[26]Zuo X,Chang K,Zhao J,et al.Bubble-template-assisted synthesis of hollow fullerene-like MoS2 nanocages as a lithium ion battery anode material[J].Journal of Materials Chemistry A,2016,4(1):51-58.