稳定且宽电位窗口的掺铁二氧化锰超级电容器材料
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摘要
利用简单的液相沉淀法制备出不同掺杂铁含量的二氧化锰超级电容器材料,旨在改善二氧化锰材料的电位窗口及稳定性。通过XRD、SEM和BET对其结构和形貌进行了表征,同时在中性电解液中采用循环伏安曲线(CV)、充放电曲线(PT)、循环性能测试、大电流充放电测试以及交流阻抗测试研究了其电化学性能。结构和形貌表征结果显示Mn/Fe-2.0具有较优的晶体结构和多孔特性,电化学测试结果显示Mn/Fe-2.0在中性电解质中表现出最好的电容性能,比电容可达489F/g,比未掺杂的纯二氧化锰材料提高了22%,同时具备稳定且宽的电位窗口,是超级电容器比较理想的正极材料。
Fe-doped manganese dioxide were synthesized via a simple liquid-phase process in order to improve its potential-window and stability. The phase structure, morphology, and size of the prepared manganese dioxide were characterized by using X-ray diffraction, scanning electron microscopy, and N_2 adsorption-desorption isotherm and the electrochemical properties of the Fe-doped manganese dioxidewere investigated by cyclic voltammetry(CV), galvanostatic charge-discharge(PT), cyclic performancetest, the high-rate discharge ability and alternating current(AC) impedance spectroscopy. The structureand morphology measurements showed Mn/Fe-2.0 were porous and had good crystal structure.Electrochemical measurements confirmed Mn/Fe-2.0 had the best capacity in neutral electrolytes, and itsspecific capacitance reached 489F/g, which increased by 22% compared to that of pure manganese dioxide. Therefore, Mn/Fe-2.0 could be an ideal anode material with a wide-potential-window and good cycling stabilities for supercapacitors.
Fe-doped manganese dioxide were synthesized via a simple liquid-phase process in order to improve its potential-window and stability. The phase structure, morphology, and size of the prepared manganese dioxide were characterized by using X-ray diffraction, scanning electron microscopy, and N_2 adsorption-desorption isotherm and the electrochemical properties of the Fe-doped manganese dioxidewere investigated by cyclic voltammetry(CV), galvanostatic charge-discharge(PT), cyclic performancetest, the high-rate discharge ability and alternating current(AC) impedance spectroscopy. The structureand morphology measurements showed Mn/Fe-2.0 were porous and had good crystal structure.Electrochemical measurements confirmed Mn/Fe-2.0 had the best capacity in neutral electrolytes, and itsspecific capacitance reached 489F/g, which increased by 22% compared to that of pure manganese dioxide. Therefore, Mn/Fe-2.0 could be an ideal anode material with a wide-potential-window and good cycling stabilities for supercapacitors.
引文
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[12] LEI Y, DAFFOS B, TABERNA P L, et al. MnO2-coated Ninanorods:enhanced high rate behavior in pseudo-capacitivesupercapacitor[J]. Electrochimica Acta, 2010, 55(25):7454-7459.
[13]陈俊明,岳刚,马莹莹,等.乙二醇为还原剂制备铁掺杂二氧化锰及其电容特性研究[J].硅酸盐通报, 2016, 6(35):1873-1876.CHEN Junming, YUE Gang, MA Yingying, et al. Enhancedelectrochemical properties of Fe-doped manganese oxidessynthesized using glocol as reductant[J]. Bulletin of the ChineseCeramic Society, 2016, 6(35):1873-1876.-MnO2
[14]林煦呐,宋朝霞,刘伟,等. Fe掺杂二氧化锰纳米棒的制备及其电化学性能[J].电源技术, 2016, 6(40):1225-1227.LIN Xuna, SONG Zhaoxia, LIU wei, et al. Preparation andelectrochemical performance of Fe-doped manganese dioxidenanorods for supercapacitors[J]. Journal of Power Sources, 2016, 6(40):1225-1227.
[15]刘卯成.双金属氧化物及其复合材料的赝电容行为研究[D].兰州:兰州理工大学, 2013.LIU Maocheng. Study on pseudo-capacitive properties of binarymetal oxides and their composite materials[D]. Lanzhou:LanzhouUniversity of Technology, 2013.
[16] XU Caijun, LI Baohua, DU Hongda, et al. Supercapacitive studies on amorphous MnO2in mild solutions[J]. Journal of Power Source,2008, 184(2):691-694.
[17]秦继伟.铁掺杂纳米二氧化锰的制备及其电化学性能[D].大连:大连理工大学, 2012.QIN Jiwei. Preparation and electrochemical performance of Fe-doped nano-MnO2[D]. Dalian:Dalian University of Technology,2012.
[18]张孟.超级电容器电极材料MnO2的结构及其电化学性能研究[D].芜湖:安徽工程大学, 2014.ZHANG Meng. Research on the structure of super capacitorelectrode materials MnO2and its electrochemical performance[D].Wuhu:Anhei Polytechenical University, 2014.
[2] ADELKHANI H, GHAEMI M. Characterization of manganesedioxide electrodeposited by pulse and direct current forelectrochemical capacitor[J]. Journal of Alloys and Compounds.2010, 493(1/2):175-178.
[3] KONG Lingbin, BAI Ruijuan, LANG Junwei, et al. The rods likemanganese dioxide films grown on nickel foam for electrochemicalcapacitor applications[J]. Russian Journal of Electrochemistry,2013, 10(49):975-982.
[4]白瑞娟.电沉积法制备镍、锰氧化物及其超级电容性能的研究[D].兰州:兰州理工大学, 2011.BAI Ruijuan. Electrochemically deposited NiO and MnO2filmswith excellent electrochemical capacitive behavior[D]. Lanzhou:Lanzhou University of Technology, 2011.
[5] LI Yang, XIE Huaqing, WANG Jifeng, et al. Preparation andelectrochemical:performances ofαnanorod forsupercapacitor[J]. Material Letters, 2011, 65(5):403-405.
[6] DUBAL D P, LOKHANDE C D. Significant improvement in theelectrochemical performances of nano-nest like amorphous MnO2electrodes due to Fe doping[J]. Ceramics International, 2013, 39(1):415-423.
[7] DONG Ruiting, YE Qinglan, KUANG Lili, et al. Enhancedsupercapacitor performance of Mn3O4nanocrystals by dopingtransition-metal ions[J]. ACS Appl. Mater. Interfaces, 2013, 5(19), 9508-9516.
[8] WANG Hongen, LU Zhonguang, QIAN Dong, et al. Facilesynthesis and electrochemical characterization of hierarchicalα-MnO2spheres[J]. Journal of Alloys and Compounds, 2008, 466,250-257.
[9]马琳.用于非对称超级电容器正极的铝掺杂二氧化锰的研究[D].大连:大连理工大学, 2012.MA Lin. A study of Al-doped MnO2used for the positive electrodeof asymmetric supercapacitor[D]. Dalian:Dalian University ofTechnology, 2012.
[10]李晓峰,黄志刚,宋海香,等.铋改性二氧化锰在电化学电容器中的应用[J].电源技术, 2015, 6(235):1251-1253.LI Xiaofeng, HUANG Zhigang, SONG Haixiang, et al. Applicationof Bi2O3coated MnO2in electrochemical capacitors[J]. ChineseJournal of Power Sources, 2015, 6(235):1251-1253.
[11] WANG Jiangan, YANG Ying, HUANG Zhenghong, et al. Effect ofFe3+on the sysnthesis and electrochemical performance ofnanostructured MnO2[J]. Materials Chemistry and Physics, 2012,133(1):437-444.
[12] LEI Y, DAFFOS B, TABERNA P L, et al. MnO2-coated Ninanorods:enhanced high rate behavior in pseudo-capacitivesupercapacitor[J]. Electrochimica Acta, 2010, 55(25):7454-7459.
[13]陈俊明,岳刚,马莹莹,等.乙二醇为还原剂制备铁掺杂二氧化锰及其电容特性研究[J].硅酸盐通报, 2016, 6(35):1873-1876.CHEN Junming, YUE Gang, MA Yingying, et al. Enhancedelectrochemical properties of Fe-doped manganese oxidessynthesized using glocol as reductant[J]. Bulletin of the ChineseCeramic Society, 2016, 6(35):1873-1876.-MnO2
[14]林煦呐,宋朝霞,刘伟,等. Fe掺杂二氧化锰纳米棒的制备及其电化学性能[J].电源技术, 2016, 6(40):1225-1227.LIN Xuna, SONG Zhaoxia, LIU wei, et al. Preparation andelectrochemical performance of Fe-doped manganese dioxidenanorods for supercapacitors[J]. Journal of Power Sources, 2016, 6(40):1225-1227.
[15]刘卯成.双金属氧化物及其复合材料的赝电容行为研究[D].兰州:兰州理工大学, 2013.LIU Maocheng. Study on pseudo-capacitive properties of binarymetal oxides and their composite materials[D]. Lanzhou:LanzhouUniversity of Technology, 2013.
[16] XU Caijun, LI Baohua, DU Hongda, et al. Supercapacitive studies on amorphous MnO2in mild solutions[J]. Journal of Power Source,2008, 184(2):691-694.
[17]秦继伟.铁掺杂纳米二氧化锰的制备及其电化学性能[D].大连:大连理工大学, 2012.QIN Jiwei. Preparation and electrochemical performance of Fe-doped nano-MnO2[D]. Dalian:Dalian University of Technology,2012.
[18]张孟.超级电容器电极材料MnO2的结构及其电化学性能研究[D].芜湖:安徽工程大学, 2014.ZHANG Meng. Research on the structure of super capacitorelectrode materials MnO2and its electrochemical performance[D].Wuhu:Anhei Polytechenical University, 2014.
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