超级电容器活性炭/MnO_2复合电极材料的制备及性能
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摘要
KMnO_4和MnCl_2在140℃反应釜中反应6h并掺杂不同含量的活性炭,经球磨后制备成超级电容器活性炭/MnO2复合电极材料。通过BET测试得出,当活性炭含量为29%(质量分数,下同)时,复合电极材料的比表面积为451m~2/g。XRD结果表明,复合物的物相结构主要为非晶。SEM结果表明,复合电极的形貌为细小环绕微纳米绒球。XPS谱线表明不同活性炭含量的复合物中均含有Mn~(4+)。当扫描速率为50 mV/s时,复合电极的比电容值达365F/g,充放电效率为93%,等效串联电阻值仅为0.87Ω。经3 000次循环后,复合电极中均出现不同程度的晶体相,电极形貌变成颗粒状和块状,但复合粒子的均匀性增强,比电容值仅下降约6%。
KMnO_4 reacted with MnCl_2 while doped different activated carbon in reaction kettle at 140℃ for 6 h,then composite electrode materials for supercapacitor were prepared after ball mill.Specific surface area of 451 m2/g was obtained through BET mehtod for content of 29 wt% activated carbon.XRD result revealed that MnO_2/activated carbon composite were hydrated and amorphous.Morphology of composite was tiny and surrounded micro-nanometer pompon globe by SEM.XPS spectrum showed composite existence of Mn~(4+) in oxide form.Specific capacitance of the electrode reached 365 F/g when scan rate was 50 mV/s,and charge-discharge efficiency was 93% as well as equivalent series resistance value of 0.87Ω.Composite electrode appeared crystal phase with different degree after 3 000 cycles,meanwhile,morphology of the electrode turned into particles and block,and capacitance value of the electrode decayed to only approximate 6%.
KMnO_4 reacted with MnCl_2 while doped different activated carbon in reaction kettle at 140℃ for 6 h,then composite electrode materials for supercapacitor were prepared after ball mill.Specific surface area of 451 m2/g was obtained through BET mehtod for content of 29 wt% activated carbon.XRD result revealed that MnO_2/activated carbon composite were hydrated and amorphous.Morphology of composite was tiny and surrounded micro-nanometer pompon globe by SEM.XPS spectrum showed composite existence of Mn~(4+) in oxide form.Specific capacitance of the electrode reached 365 F/g when scan rate was 50 mV/s,and charge-discharge efficiency was 93% as well as equivalent series resistance value of 0.87Ω.Composite electrode appeared crystal phase with different degree after 3 000 cycles,meanwhile,morphology of the electrode turned into particles and block,and capacitance value of the electrode decayed to only approximate 6%.
引文
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23 Xiong Y C,Zhou M,Chen H,et al.Synthesis of honeycomb MnO2nanospheres/carbon nanoparticles/grap here composite as super capaciotrs electrode materials[J].Applied Surface Science,2015,357:1024.
2 Izadi N,Yasuda A S,Futaba K Y,et al.Extracting the full potential of single-walled carbon nanotubes as durable super-capacitors electrodes operable at 4V with high power and energy density[J].Advanced Materials,2010,22:E235.
3 Conway B E.陈艾,吴梦强,张绪礼,等译.电化学电容器的科学原理及技术应用[M].北京:化学工业出版社,2005.
4 Ruiza V,Blancoa C,Santamaria R,et al.An activated carbon monolith as an electrode material for supercapacitors[J].Carbon,2009,47:195.
5 Kuo S L,Wu N L.Composite supercapacitor containing tin oxide and electro-plated ruthenium oxide[J].Electrochemical and SolidState Letters,2003,6:A85.
6 Li X,Gan W P,Zhang W C,et al.Polyaniline/RuO2composite electrode prepared by thermal decomposition and electro-chemistry polymerization procedures[J].Acta Materiae Compositae Sinica,2012,29(5):1(in Chinese).李祥,甘卫平,张文超,等.涂敷热分解及电化学聚合法制备氧化钌/聚苯胺复合电极[J].复合材料学报,2012,29(5):1.
7 Snook G A,Kao P,Best A S.Conducting-polymer-based supercapacitor devices and electrodes[J].Journal of Power Sources,2011,157:1.
8 Li X,Gan W P,Ma H R,et al.Preparation and properties of 60%RuO2-AC composite electrode materials by the colloidal[J].Acta Materiae Compositae Sinica,2011,28(3):90(in Chinese).李祥,甘卫平,马贺然,等.胶体法制备60%RuO2/AC复合电极材料及其性能[J].复合材料学报,2011,28(3):90.
9 Yan Y,Xu H,Guo W,et al.Facile synthesis of amorphous aluminum vanadate hierarchical microspheres for supercapacitors[J].Inorganic Chemistry Frontiers,2016,3:791.
10 Yan Y,Xu H,Guo W,et al.Vanadium based materials as electrode materials for high performance supercapacitors[J].Journal of Power Sources,2016,329:148.
11 Yan Y,Xu H,Zheng S S,et al.Facile synthesis of an accordion-like Ni-MOF superstructure for high-performance flexible supercapacitors[J].Journal of Materials Chemistry A,2016,4:19078.
12 Sutrave D S,Joshi P S,Gothe S D,et al.Structural and morphological properties of ruthenium oxide thin films deposited by sol-gel spin coating[J].International Journal of ChemTech Research,2014,6(3):1991.
13 Liu H,Gan W P,Huang B,et al.Preparation of doped tin ruthenium oxide film electrode for supercapacotor[J].Rare Metal Material and Engineering,2011,40(1):115(in Chinese).刘泓,甘卫平,黄波,等.掺锡氧化钌超级电容器薄膜电极的研制[J].稀有金属材料与工程,2011,40(1):115.
14 Ma W J,Chen S H,Yang S Y,et al.Hierarchical MnO2nanowires/graphene hybrid fibers with excellent electro-chemical perfor-mance for flexible solid-state supercapacitors[J].Jouranl of Power Sources,2016,306:481.
15 Rakhi R B,Chen W,Hedhili M N,et al.Enhanced rate performance of meso-porous Co3O4nanosheet super-capacitor electrode by hydrous RuO2 nanoparticle decoration[J].ACS Applied Materials Interfaces,2014,6:4196.
16 Yan Y,Wang T Y,Li X R,et al.Noble metal-based materials in high-performance supercapacitors[J].Inorganic Chemistry Frontiers,2017,4:33.
17 Xiong Y C,Zhou M,Chen H,et al.Synthesis of honeycomb MnO2nano spheres/carbon nanoparticles/graphene composites as electrode materials for supercapacitors[J].Applied Surface Science,2015,357:1024.
18 Lee D G,Kim J H,Kim B H.Hierarchical porous MnO2/carbon nanofiber composite with hollow cores for high performance supercapacitor electrodes:Effect of poly(methacrylate)concentration[J].Electrochimica Acta,2016,200:174.
19 Vinny R T,Chaitra K,Krishna V,et al.An excellent cycle performance of asymmetric supercapacitor based on bristles likeα-MnO2[J].Journal of Power Sources,2016,309:212.
20 Chen W Y,Tao X Q,Wei D H.High performance supercapacitor based activated-MnO2-polyanilinecomposite[J].Journal of Materials Science-Materials in Electronics,2016,27:1357.
21 Fu C J,Li S,Song C L,et al.Preparation of polypyrrol/graphite oxide composite and its capacitive properties[J].Acta Materiae Compositae Sinica,2016,33(3):572(in Chinese).付长璟,李爽,宋春来,等.聚吡咯/氧化石墨烯复合材料的制备及其电容性能[J].复合材料学报,2016,33(3):572.
22 Gao G P,Lu A H,Li W C.Dual functions of activated carbon in positive electrode for MnO2 based supercapacitors[J].Journal of Power Sources,2011,196:4095.
23 Xiong Y C,Zhou M,Chen H,et al.Synthesis of honeycomb MnO2nanospheres/carbon nanoparticles/grap here composite as super capaciotrs electrode materials[J].Applied Surface Science,2015,357:1024.