二氧化钌基复合氧化物电极材料电化学电容性能的研究
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摘要
本文采用热分解氧化法制备了不同组成的Ti/RuO_2-SnO_2二元氧化物和Ti/RuO_2-TiO_2-SnO_2三元氧化物复合电极材料,用XRD、SEM和电化学测试方法研究了电极材料的结构、表面形貌及其赝电容性能。研究结果表明,在相同活性涂层质量下,随着复合金属氧化物中RuO_2含量的降低,RuO_2基复合氧化物电极材料比电容也随之减小,但在适当的RuO_2含量时电极仍具有较大的比电容。当RuO_2在涂层中的含量为30%(mol)时,Ti/RuO_2-SnO_2电极和Ti/RuO_2-TiO_2-SnO_2三元氧化物复合电极都具有良好的赝电容性能。在相同含钌量下,Ti/Ru_(0.3)Ti_(0.7-x)Sn_xO_2电极的电容性能优于Ti/Ru_(0.3)Sn_(0.7)O_2电极。比较活性涂层质量相近的Ti/Ru_(0.3)Ti_(0.7-x)Sn_xO_2,Ti/Ru0.3Sn0.7O_2和Ti/RuO_2的电容性能,发现掺杂SnO_2或SnO_2+TiO_2的方法制备的RuO_2基氧化物复合电极的赝电容性能虽然略差于纯Ti/RuO_2电极,但减少了RuO_2用量。Ti/Ru_(0.3)Ti_(0.7-x)Sn_xO_2电极的比电容随RuO_2含量不按比例增大。
The key to effect the performance of supercapacitor is the characteristics of electrode materials for supercapacitor,the purpose of research is focus on how to prepare electrode materials with high-energy density,high specific capacity and long cycle life. Based on pseudo-capacitive mechanism of charge storage reaction, Ruthenium oxide is an ideal electrode material of supercapacitor with high specific capacity and energy density,the CV curve in sulfuric acid is close to rectangle. However, some disadvatanges of ruthenium oxide such as cost, environmental pollution limit its wide application in the industry. The purpose of this dissertation is mainly based on adding the other metal oxide to form composite metal oxides.due to good properties of SnO_2 and TiO_2 , in this study we doped SnO_2 and TiO_2 to ruthenium oxide as electrode materials for supercapacitor with low cost ,high specific capacity, good stability.
Different composition ratio mixed Ti/RuO_2-SnO_2 and Ti/RuO_2-TiO_2-SnO_2electrodes are prepared by thermal decomposition, and the crystalline structure、morphology and pseudo- capacitive characteristics are characterized by XRD、SEM and other electrochemical methods.The results shows there are no significant diffraction peaks of RuO_2 and SnO_2 even more added with TiO_2 because RuO_2 and SnO_2 form solid solution, the oxide surface morphology shows mud-?at cracking with an agglomerated structure.When the content of oxides added is higher ,the value of specific capataince is decreased.When the molar ratio of RuO_2 is 30%, the pseudo-capacitive characteristics of Ti/RuO_2-SnO_2 and Ti/RuO_2-TiO_2-SnO_2 compound oxide electrodes all possess high electrochemical reversibility. In the case of the same amount of RuO_2 ,the capacitive property of Ti/Ru_(0.3)Ti_(0.7-x)Sn_xO_2 electrodes are better than Ti/Ru_(0.3)Sn_(0.7)O_2.We contrast the following electrodes with the same quality of active coating,Ti/Ru_(0.3)Ti_(0.7-x)Sn_xO_2,Ti/Ru_(0.3)Sn_(0.7)O_2 and Ti/RuO_2,the resulst shows pseudo- capacitive characteristics of RuO_2-based composite oxide electrodes doping with SnO_2 and SnO_2+TiO_2 are worse than Ti/RuO_2 without other oxides,however the amount of RuO_2 is decreased.While the amount of RuO_2 are reduced, specific capataince of Ti/ Ru_(0.3)Ti_(0.7-x)Sn_xO_2 do not remain proportional decrease .
The key to effect the performance of supercapacitor is the characteristics of electrode materials for supercapacitor,the purpose of research is focus on how to prepare electrode materials with high-energy density,high specific capacity and long cycle life. Based on pseudo-capacitive mechanism of charge storage reaction, Ruthenium oxide is an ideal electrode material of supercapacitor with high specific capacity and energy density,the CV curve in sulfuric acid is close to rectangle. However, some disadvatanges of ruthenium oxide such as cost, environmental pollution limit its wide application in the industry. The purpose of this dissertation is mainly based on adding the other metal oxide to form composite metal oxides.due to good properties of SnO_2 and TiO_2 , in this study we doped SnO_2 and TiO_2 to ruthenium oxide as electrode materials for supercapacitor with low cost ,high specific capacity, good stability.
Different composition ratio mixed Ti/RuO_2-SnO_2 and Ti/RuO_2-TiO_2-SnO_2electrodes are prepared by thermal decomposition, and the crystalline structure、morphology and pseudo- capacitive characteristics are characterized by XRD、SEM and other electrochemical methods.The results shows there are no significant diffraction peaks of RuO_2 and SnO_2 even more added with TiO_2 because RuO_2 and SnO_2 form solid solution, the oxide surface morphology shows mud-?at cracking with an agglomerated structure.When the content of oxides added is higher ,the value of specific capataince is decreased.When the molar ratio of RuO_2 is 30%, the pseudo-capacitive characteristics of Ti/RuO_2-SnO_2 and Ti/RuO_2-TiO_2-SnO_2 compound oxide electrodes all possess high electrochemical reversibility. In the case of the same amount of RuO_2 ,the capacitive property of Ti/Ru_(0.3)Ti_(0.7-x)Sn_xO_2 electrodes are better than Ti/Ru_(0.3)Sn_(0.7)O_2.We contrast the following electrodes with the same quality of active coating,Ti/Ru_(0.3)Ti_(0.7-x)Sn_xO_2,Ti/Ru_(0.3)Sn_(0.7)O_2 and Ti/RuO_2,the resulst shows pseudo- capacitive characteristics of RuO_2-based composite oxide electrodes doping with SnO_2 and SnO_2+TiO_2 are worse than Ti/RuO_2 without other oxides,however the amount of RuO_2 is decreased.While the amount of RuO_2 are reduced, specific capataince of Ti/ Ru_(0.3)Ti_(0.7-x)Sn_xO_2 do not remain proportional decrease .
引文
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[2]B.E.Conway.Electrochemical Supercapacitors Scientific Fundamentals and Technological Applica-tions[J].New York:Plenum Press,1999
[3]R..Ko¨tz a,*, M.Carlen b. Principles and applications of electrochemical capacitors[J]. ElectrochimicaActa ,45 (2000) 2483–2498
[4]PatrieeS,YurGotsi.MaterialsforElectrochemicalCaPacitors[J].NatureMaterials,2008,7:845-854
[5]Robert A. Huggins. Supercapacitors and electrochemical pulse sources[J]. Solid State Ionics ,134(2000) 179–195
[6]B.E.Conway .电化学超级电容器-科学原理及技术应用[M].陈艾译.北京.化学工业出版社，2005.9-14
[7]Qu D Y.Stuies of actived carbons used in double-layer supercapacitors[J].J.Power Sources, 2002,109(2):403~411.
[8]Conway B E.Transition from“supercapacitor”to“battery”behavior in electrochemical energystorage[J].J.Electrochem.Soc.,1991,138(6):1539~1548
[9]Zheng J P,Jow T R.A new charge storage mechanism for electrochemical capacitors[J].Electro-chem.Soc,1995,142(1):L6~L8.
[10]钟海云，李荐，戴艳阳等，新型能源器件－超级电容器研究发展最新动态[J],电源技术,2001,25(5):367-370.
[11]肖芳，复合金属氧化物材料的电化学电容行为[D].新疆大学,2005
[12] Jarvis, L.P.Atwater, T.B.Cygan, P.J,Hybrid power sources for Land Warrior scenario, Power Sources,1999, 79, 60–63.
[13]Faggioli E,Rena P,Danel V.Supercapcitors for the energy management for electric vehicles[J PowerSources,1999,84,261～169
[14]Nishino A.Capacitors:operating principles,current market and technical trends[J]. PowerSources ,1996,60:137~147.
[15]Schaller K V,Gruber C.Fuel cell drive and high dynamic energy storage systems Oppor-tunities forthe future city bus[J].Fuel Cells Bulletin,2000,3(27):9~13.
[16]Fair H.et al,The science and technology of electric launch:A U.S.perspective,IEEETRans. MAG[J].1999,35(1):11~18.
[17]B.E.Conway,V.Birss,J.Wojtowicz..The Role and Utilization of Pseudocapacitance for EnergyStorage by Supercapacitors.Journal of Power Sources[J],1997,(66):1-14
[18]王晓峰，解晶莹，孔祥华等.“超电容”电化学电容器研究进展.电源技术[J].2001,25(5): 166一170
[19]B.E.Conway.Transition from“Supereapaeitor”to“Battery”Behavior in Electrochemical EnergyStorage[J].Journal of The Electroehemical Soeiety,1991,138(6):1539一1548.
[20]B.E.Conway,电化学超级电容器-科学原理及技术应用[M].陈艾译.北京.化学工业出版社，2005.200-210.
[21]Andrew Burke*，Ultracapacitors: why, how, and where is the technology[J].Journal of PowerSources 91_2000.37–50
[22]Y.H. Lee, H.S. Kim, W.K. Seong, S.W. Kim, Electrochemical oxide pseudocapacitor working in amild aqueous electrolyte, Proceedings of the 9th International Seminar on Double-layer Capacitors andSimilar Energy Storage Devices[J].Deerfield Beach, FL, December1999.
[23]Conway B E, Pell W G. Double一layer and pseudo-capacitance types of electrochemical capacitorsand their applications to the development of hyrid deveces. [J].Solid State Eleetrochem., 2003,7:637一644
[24]郎俊伟,，高容量金属氧化物超级电容器电极材料的制备与性能研究[D].兰州理工大学,2008
[25]Ren,X,S.Gottesfeld.J.P.Ferraris.in:F.M.Delinck.M.Tomkiewocz(Eds.).“Electrochemical Capacitors:Proceedings”[J].The Electrochemical Society:Pennigton,NJ:p.138.1996
[26]Arbizzani.C,M.Mastragostino.LMeneghello.Polyer-based redox supercapacitors：Acomparativestudy”[J].Electrochim.Acta.41,21-26
[27]张治安，杨邦朝，金属氧化物超大容量电容器电极材料的研究进展[J].材料导报，2004.2,17 (18),30-33
[28]杨惠,石兆辉,金属氧化物超级电容器的研究进展[J]. 2005.35(6),477-479
[29]Barbara Marie Djurfors, Microstructural Characterization of Porous Thin Films and Applications toElectrochemical Capacitors[D].University of Alberta,2005
[30]原长洲，钴镍金属氧化物及混合超级电容器的电化学电容行为[D].新疆大学,2005
[31]Katsunori Yokoshima, Electrochemical supercapacitor behavior of nanoparticulate rutile-typeRu1?xVxO2[J]. Journal of Power Sources 160 (2006) 1480–1486
[32]M.Min,K.Machida,J.H.Jang,K.Naoi,Effect of Electronic Resistance and Water Content on thePerformance of RuO2 for Supercapacitors[J].Electrochem.Soc.,2006,153,A334
[33]林志东，超级电容器氧化物电极材料研究进展[J] .2005,27( 2)40-43
[34]Raiistrick ID. The electrochem istryof sem iconductors and electronics p rocesses and devices [M ].N ewJersey: L uduing F Noyes, 1992.
[35]ZhengJ P , Jow T R . Ruthenium oxide film electrodes prepared at low temperatures for electrochemical capacitors [J ]. J Electrochem Soc, 1995, 142: L 6-L 8.
[36]M.A.Anderson,S.C.Pang,T.W.Chapman,Novel Electrode Materiel for Thin-film Ultracapacitors:Comparison of Electrochemical Properties of Sol-gel-drived and Electrode Deposited ManganeseDioxide [J].Electrochem.Soc,2000,147(2),444
[37]J.N. Broughton, Variations in MnO2 electrodeposition for electrochemical capacitors[J]. Electro-chimica Acta 50 (2005) 4814–4819
[38]Zheng J P,Jow T R.A New Charge Storage Mechanism for Electrochemical Capacitors[J]. Electr-oanal Chem.1995,142(1):6～8
[39]梁逵，陈艾，吴孟强等.热处理温度及掺杂对氧化镍电极厥电容器特性的影响[J].硅酸盐学报,2002,30(1):1~4.
[40]Lin C , Ritter A J , Popov N B.Characterization of sol-gel-derived cobalt oxide xerogels as electro-chemical capacitors [ J ] .Elctrochem Soc ,1998 ,145 (12) :4 097 - 4 1031
[41]Machefaux E,Brousse T,Bélanger D and Guyomard D.Supercapacitor behavior of new substitutedmanganese dioxides[J].J.Power Sources,2007,165(2):651~655.
[42]Wang Y G and Xia Y Y.Electrochemical capacitance characterization of NiO with ordered Mesop-orous structure synthesized by template SBA-15[J].Electrochim.Acta,2006,51(16):3223~3227.
[43]H.-S Hwang. Effect of Charge and Discharge on the Capacitance of Supercapacitor of HydrousRuthenium Oxides and Carbon Nanotube Coatings[J] .Microsc Microanal ,2008,14(2),332-333
[44]Wei-Chuan Fang, Oliver Chyan, Arrayed CNx NT–RuO2 nanocomposites directly grown on Tibuffered Si substrate for supercapacitor applications[J]. Electrochemistry Communications ,(2007)239–244
[45]Rak Young Song, Jun Ho Park. Supercapacitive properties of polyaniline/Nafion/hydrous RuO2composite electrodes[J]. Journal of Power Sources 166 (2007) 297–301
[46]Chi-Chang Hu*, Ta-Wang Tsou.Capacitive and textural characteristics of hydrous manganese oxideprepared by anodic deposition[J]. Electrochimica Acta ,47 (2002) 3523～3532
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