熔盐法处理废旧聚丙烯腈纤维制备超级电容器碳材料及性能表征
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摘要
以废旧纺织品聚丙烯腈为碳源,在氯化锌-氯化钾熔盐体系一步碳化活化制备超级电容器碳材料.通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、比表面分析仪等物理测试方法对材料进行结构、形貌和孔隙表征.并利用电化学工作站在三电极体系下对制备的碳材料进行循环伏安(CV)、恒流充放电(GCD)和交流阻抗(EIS)测试.结果表明,通过在空气中200℃稳定化10 h、氯化锌-氯化钾熔盐体系中800℃下炭化2 h制备的活性炭具有较大的比表面积和发达的孔结构,作为超级电容器电极材料展现出优异的电化学性能.在0. 25 A/g电流密度下最大比电容达319 F/g;在电流密度高达10 A/g下,比电容仍保留62. 7%.经过5 000次充放电循环性能测试,容量保持率可达82. 6%.
In this work,the waste polyacrylonitrile fibers were used as the carbon source,and the carbonization and activation process were conducted to produce capacitance carbon with one-step in molten ZnCl_2-KCl system. The phase crystalline, morphology and pore structure were characterized by X-ray diffraction( XRD), scanning electron microscopy( SEM), and specific surface area analysis. The electrochemical properties of the prepared carbon materials were tested by cyclic voltammetry( CV),galvanostatic charge-discharge( GCD) and electrochemical impedance spectroscopy( EIS),and the test was performed by a Princeton electrochemical workstation. The results show that the activated carbon material was successfully prepared by stabilization at 200 ℃ for 10 h in air and carbonization 800 ℃ in a ZnCl_2-KCl system. It also possesses a high specific surface area and excellent pore structure. The as-prepared activated carbon displays good electrochemical performance with specific capacitance of 319 F/g at a current density of 0. 25 A/g and good high rate discharge capacity with a retention of 62. 7% at a current density of 10 A/g.Also,the charge-discharge cycling performance of 5 000 cycles can retain 82. 6% of the first cycle.
In this work,the waste polyacrylonitrile fibers were used as the carbon source,and the carbonization and activation process were conducted to produce capacitance carbon with one-step in molten ZnCl_2-KCl system. The phase crystalline, morphology and pore structure were characterized by X-ray diffraction( XRD), scanning electron microscopy( SEM), and specific surface area analysis. The electrochemical properties of the prepared carbon materials were tested by cyclic voltammetry( CV),galvanostatic charge-discharge( GCD) and electrochemical impedance spectroscopy( EIS),and the test was performed by a Princeton electrochemical workstation. The results show that the activated carbon material was successfully prepared by stabilization at 200 ℃ for 10 h in air and carbonization 800 ℃ in a ZnCl_2-KCl system. It also possesses a high specific surface area and excellent pore structure. The as-prepared activated carbon displays good electrochemical performance with specific capacitance of 319 F/g at a current density of 0. 25 A/g and good high rate discharge capacity with a retention of 62. 7% at a current density of 10 A/g.Also,the charge-discharge cycling performance of 5 000 cycles can retain 82. 6% of the first cycle.
引文
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[2]Xu Z,Yuan Z,Zhang D,et al.Highly mesoporous activated carbon synthesized by pyrolysis of waste polyester textiles and MgCl2:physiochemical characteristics and pore-forming mechanism[J].Journal of Cleaner Production,2018,192:453-461.
[3]Zhang J,Zhao X,Huang Z,et al.High-performance all-solid-state flexible supercapacitors based on manganese dioxide/carbon fibers[J].Carbon,2016,107:844-851.
[4]Li Z,Huang T,Gao W,et al.Hydrothermally activated graphene fiber fabrics for textile electrodes of supercapacitors[J].ACS Nano,2017,11(11):11056 1065.
[5]Obreja V V N.On the performance of supercapacitors with electrodes based on carbon nanotubes and carbon activated material-A review[J].Physica E:Low-dimensional Systems and Nanostructures,2008,40(7):2596-2605.
[6]Zhang Q,Han K,Li S,et al.Synthesis of garlic skin-derived 3D hierarchical porous carbon for high-performance supercapacitors[J].Nanoscale,2018,10(5):2427-2437.
[7]秦川丽,董楠,谭强,等.KOH活化对超级电容器用活性炭的影响[J].黑龙江大学自然科学学报,2009,26(1):35-38.
[8]Wang C,Sun L,Zhou Y,et al.P/N co-doped microporous carbons from H3PO4-doped polyaniline by in situ activation for supercapacitors[J].Carbon,2013,59:537-546.
[9]Deng X,Zhao B,Zhu L,et al.Molten salt synthesis of nitrogen-doped carbon with hierarchical pore structures for use as high-performance electrodes in supercapacitors[J].Carbon,2015,93:48-58.
[10]Ouyang T,Cheng K,Gao Y,et al.Molten salt synthesis of nitrogen doped porous carbon:a new preparation methodology for high-volumetric capacitance electrode materials[J].Journal of Materials Chemistry A,2016,4(25):9832-9843.
[11]Cheng Y,Li B,Huang Y,et al.Molten salt synthesis of nitrogen and oxygen enriched hierarchically porous carbons derived from biomass via rapid microwave carbonization for high voltage supercapacitors[J].Applied Surface Science,2018,439:712-723.
[12]邓文.聚丙烯腈的阻燃和热分解研究[D].上海:东华大学,2010.
[13]白雪.回收利用率不到万分之三废旧纺织品富矿待挖[J].中国战略新兴产业,2014(8):74-75.
[14]晏晓东.磷掺杂聚丙烯腈基碳材料的制备及其在超级电容器中的应用[D].北京:北京化工大学,2014.
[15]Hao R,Yang Y,Wang H,et al.Direct chitin conversion to N-doped amorphous carbon nanofibers for high-performing full sodium-ion batteries[J].Nano Energy,2018,45:220-228.
[16]Li Y,Wang G,Wei T,et al.Nitrogen and sulfur co-doped porous carbon nanosheets derived from willow catkin for supercapacitors[J].Nano Energy,2016,19:165-175.