Abstract: Nowadays, the energy issue has increasingly become a hot spot of social attention, and the supercapacitor as a new type of energy storage device attracts much attention due to its long service life, high power and environmental friendliness. MnO2 based supercapacitors not only assume the characteristics of high power density, long cycle life, fast charge and discharge, but also have the advantages of low cost, broad source and environmental friendliness. Thus they have displayed a very broad application prospects and economic value in various fields. However, the specific capacitance of the MnO2 based supercapacitor is considerably lower than the theoretical value due to its poor conductivity and limited specific surface area. Moreover, its unstable structure also results in poor cycling stability. To resolve the above mentioned problems, the current researches about the MnO2 based supercapacitor mainly focus on finding facile and controllable preparation methods to improve the electrochemical properties like conductivity, specific capacitance, cycling stability, etc., and trying to magnify the advantages and realize synergistic effect of various electrode materials. Searching a simple and controllable electrode preparation method has become a primary task for high quality MnO2 based supercapacitors. The common methods include sol-gel method, hydrothermal synthesis method, chemical precipitation method, low temperature solid phase method and electrochemical deposition method. The resultant powders prepared by sol-gel method have high purity, agglomerate easily due to the drying conditions. Through the chemical precipitation method can obtain uniformly distributed powders with even chemical compositions, and still, ease of agglomerat owing to high synthesis temperature. The low temperature solid phase method can efficiently overcome the shortcomings mentioned above involving the rapid growth and agglomeration of particles at high temperature, but nevertheless suffers low reaction conversion rate which is attributed to the inadequate contact among the reactants. The hydrothermal synthesis is a simple and low cost method which has been applied to prepare the powder widely at pre-sent. The powders prepared by the above methods need certain pre-treatment for the fabrication of electrode, which extends the process and is detrimental to energy saving and environmental protection. On the contrary, the electrodeposition method can directly deposit manganese dioxide on different substrates with flexible operation and controllable operating parameters. The modification of manganese dioxide electrode material has converged intensive research endeavors, the doping and composing methods are still used commonly at present, for example, a small amount of metal elements doped in manganese dioxide can improve the conductivity of the electrode, and some conductive polymers added into manganese dioxide can effectively solve the unstable structure of manganese dioxide which results in its easy dissolution in the electrolyte. In order to obtain the high-quality electrode, it is very essential to select the species of the doped materials and composited materials, their proportions, and the doping and composing methods. Now, the MnO2 based supercapacitor is not barely composed of MnO2, but a combination of MnO2and other substances, such as a variety of carbon materials, composite materials or metal oxides. The combination of multiple composite materials can adequately make use of the characteristics of each component, which contributes to optimizing the performance of the capacitor. In addition, some scholars also found that the selection of electrolyte has great influence on expanding the electrochemical window of supercapacitors, improving the energy density and power density of capacitors. This paper briefly introduces the energy storage mechanism and summarizes the research status of capacitor electrolyte, electrode preparation and modification method. The fabrication and performance characteristics of MnO2 based supercapacitors device are introduced, and the future research trends are also presented.
1 Liu Fuhai, Kang Chunping, Li Zhongqiao, et al. Research progress of MnO2 as electrode materials used in supercapacitors[J].Journal of Dongguan University of Technology,2016(1):42(in Chinese). 刘福海,康春萍,李中桥,等.二氧化锰作为超级电容器电极材料的研究进展[J].东莞理工学院学报,2016(1):42. 2 He Xiaojun, Li Xiaojing, Wang Xiaoting, et al. Efficient preparation of porous carbons from coal tar pitch for high performance super capacitors[J].New Carbon Materials,2014,29(6):493. 3 Li Liang, Tan Li, Li Gengnan, et al. Insight into synergy within multi-decorated graphene 3 D networks for high performance supercapacitor[J].Journal of Solid State Chemistry,2017,251:266. 4 Güven zdemir Z, Yilmaz Canli N, Senkal B F, et al. Super-capacitive behavior of carbon nano tube doped 11-(4-cyanobiphenyl-4-oxy) undecan-1-ol[J].Journal of Molecular Liquids,2015,211:442. 5 Sun Hang, She Ping, Xu Kongliang, et al. A self-standing nanocomposite foam of polyaniline@reduced grapheme oxide for flexible super-capacitors[J].Synthetic Metals,2015,209:68. 6 Bahloul A, Nessark B, Briot E, et al. Polypyrrole-covered MnO2 as electrode material for supercapacitor[J].Journal of Power Sources, 2013,240:267. 7 Fang Wei, Chen Xiaohong, Song Huaihe, et al. Study of bamboo-based carbon/polyaniline composite used as supercapacitor electrode material[J].Carbon Techniques,2015,34(3):15(in Chinese). 方偎,陈晓红,宋怀河,等.竹炭/聚苯胺复合材料作为超级电容器电极材料的研究[J].炭素技术,2015,34(3):15. 8 Wang Pengfei, Liu Hui, Xu Yuxing, et al. Supported ultrafine ruthenium oxides with specific capacitance up to 1 099 F·g-1 for a supercapacitor[J].Electrochimica Acta,2016,194:211. 9 Yang Min Ho, Hong Seok Bok, Choi Bong Gill. Hierarchical MnO2 nanosheet arrays on carbon fiber for high-performance pseudocapacitors[J].Journal of Electroanalytical Chemistry,2015,759:95. 10 Yu Wei, Li Benqiang, Ding Shujiang. Electroless fabrication and supercapacitor performance of CNT@NiO-nanosheet composite nanotubes[J].Nanotechnology,2016,27(7):1. 11 Conway B E. Transition from “supercapacitor” to “battery” behavior in electrochemical energy storage[J].Journal of The Electrochemical Society,1991,138(6):1539. 12 Liu K C, Aanderson M A. Porous nickel oxide/nickel films for electrochemical capacitors[J].Journal of The Electrochemical Society,1996,143:124. 13 Lin C, Ritter J A, Popov B N. Characterization of sol-gel-derived cobalt oxide xerogels as electrochemical capacitors[J].Joural of The Electrochemical Society,1998,145:4097. 14 Srinivasan V, Weidner J W. An electrochemical route for making porous nickel oxide electrochemical capacitors[J].Journal of The Electrochemical Society,1997,144:L210. 15 Lee H Y, Coodenough J B. Supercapacitor behavior with KCl electrolyte[J].Journal of Solid State Chemistry,1999,144:220. 16 Arnott J B, Donne S W. Examining manganese dioxide-graphite connectivity in alkaline electrolytes[J].Journal of The Electrochemical Society,2007,154:A776. 17 Zhang Milin, Yang Chen, Chen Ye, et al. Studies on electrolyte performance of nano-MnO2 supercapacitors[J].Chinese Journal of Po-wer Sources,2004,28(10):626(in Chinese). 张密林,杨晨,陈野,等.纳米MnO2超级电容器电解液性能研究[J].电源技术,2004,28(10):626. 18 Jaidev, Jafri R I, Mishra A K, et al. Polyaniline-MnO2 nanotube hybrid nanocomposite as supercapacitor electrode material in acidic electrolyte[J].Journal of Materials Chemistry,2011,21:17601. 19 Zhu Qiancheng, Liu Kuan, Zhou Jianqing, et al. Design of a unique 3D-nanostructure to make MnO2 work assupercapacitor material in acid environment[J].Chemical Engineering Journal,2017,321:554. 20 Izan Izwan Misnon, Radhiyah Abd Aziz, Nurul Khairiyyah Mohd Zain, et al. High performance MnO2 nanoflower electrode and the relationship between solvated ion size and specific capacitance in highly conductive electrolytes[J].Materials Research Bulletin,2014,57:221. 21 Nguyen Van Hoa, Charmaine Lamiel, Nguyen Huu Nghia, et al. Different morphologies of MnO2 grown on the graphene@nickel foam electrode for supercapacitor application[J].Materials Letters,2017,208:102. 22 Do Geum Lee, Cheol Min Yang, Bo-Hye Kim. Enhanced electrochemical properties of boron functional groups on porous carbon nanofiber/MnO2 materials[J].Journal of Electroanalytical Chemistry,2017,788:192. 23 Lina Khandare, Santosh Terdale. Gold nanoparticles decorated MnO2 nanowires for high perfor-mance supercapacitor[J].Applied Surface Science,2017,418:22. 24 Xu Jing, Li Jiaqiang, Yang Qiaoling, et al. In-situ synthesis of MnO2@graphdiyne oxides nanocomposite with enhanced perfor-mance of supercapacitors[J].Electrochimica Acta,2017,251:672. 25 Luo Xin, Yang Jiaoyan, Yan Dan, et al. MnO2-decorated 3D porous carbon skeleton derived from mollusk shell for high-performance supercapacitor[J].Journal of Alloys and Compounds,2017,723:505. 26 Aghazadeh M, Asadi M, Maragheh M G, et al. Facile preparation of MnO2 nanorods and evaluation of their supercapacitive characteristics[J].Applied Surface Science,2016,364:141. 27 Zhou He, Zou Xiaopeng, Zhang Yanrong. Fabrication of TiO2@MnO2 nanotube arrays by pulsed electrodeposition and their application for high-performance supercapacitors[J].Electrochimica Acta,2016,192:259. 28 Kalubarme R S, Jadhav H S, Park C J. Electrochemical characteristics of two-dimensional nano-structured MnO2 for symmetric supercapacitor[J].Electrochimica Acta,2013,87:457. 29 Kyung Wan Nam, Chang Wook Lee, Xiao Qing Yang, et al. Electrodeposited manganese oxides on three-dimensional carbon nanotube substrate: Supercapacitive behaviour in aqueous and organic electrolytes[J].Journal of Power Sources,2009,188:323. 30 Zhang Yafei, Zhang Chuanxiang, Huang Guangxu, et al. Synthesis and capacitive properties of manganese oxide nanoparticles dispersed on hierarchical porous carbons[J].Electrochimica Acta,2015,166:107. 31 Li Y S, Sun I W, Chang J K, et al. Doped butylmethylpyrrolidi-nium-dicyanamide ionic liquid as an electrolyte for MnO2 supercapa-citors[J].Journal of Materials Chemistry.2012,22:6274. 32 Zhao Dandan, Zhao Yongqing, Zhang Xuan, et al. Application of high-performance MnO2 nanocomposite electrodes in ionic liquid hybrid supercapacitors[J].Materials Letters,2013,107:115. 33 Serkan Akbulut, Mesut Yilmaz, Supil Raina, et al. Solid-state supercapacitor cell based on 3D nanostructured MnO2/CNT microelectrode array on graphite and H3PO4/PVA electrolyte[J].Diamond & Related Materials,2017,74:222. 34 Kazushi Shimamoto, Kiyoharu Tadanaga, Masahiro Tatsumisago. All-solid-state electrochemical capacitors using MnO2/carbon nanotube composite electrode[J].Electrochimica Acta,2013,109:651. 35 Nilesh R Chodankar, Deepak P Dubal, Girish S Gund, et al. A symmetric MnO2/MnO2 flexible solid state supercapacitor operating at 1.6 V with aqueous gel electrolyte[J].Journal of Energy Chemistry,2016,25:463. 36 Long Xiao, Zeng Zhigang, Guo Erjuan, et al. Facile fabrication of all-solid-state flexible interdigitated MnO2 supercapacitor via in-situ catalytic solution route[J].Journal of Power Sources,2016,325:264. 37 Mei Xia Guo, Shao Wei Bian, Fu Shao, et al. Hydrothermal synthesis and electrochemical performance of MnO2/graphene/polyester composite electrode materials for flexible supercapacitors[J].Electrochimica Acta,2016,209:486. 38 Zhu Junjie, Yu Lili, Jin Taozhao. 3D network mesoporous beta-manganese dioxide: Template-free synthesis and supercapacitive perfor-mance[J].Journal of Power Sources,2014,270:411. 39 Wang Fuhua, Mao Zhiyou, Yao Qiushi, et al. Synthesis and supercapacitor performance of activated carbon/MnO2 composites[J].Applied Chemical Industry,2015,44(5):785. 王福华,茆志友,姚秋实,等.活性炭/二氧化锰纳米复合材料的合成及超级电容性能[J].应用化工,2015,44(5):785. 40 Adelkhania H, Ghaemi M. Characterization of manganese dioxide electrodeposited by pulse and direct current for electrochemical capacitor[J].Journal of Alloys and Compounds,2010,493:175. 41 Ashassi-Sorkhabi H, Asghari E, La’le Badakhshan P. Potentiostatic and cyclic voltammetric deposition of nanostructured manganese oxide for supercapacitor applications[J].Current Applied Physics,2014,14:187. 42 Dubala D P, Dhawalea D S, Gujarb T P, et al. Effect of different modes of electrodeposition on supercapacitive properties of MnO2 thin films[J].Applied Surface Science,2011,257:3378. 43 Yang Jie, Lian Lifang, Ruan Hongcheng, et al. Nanostructured po-rous MnO2 on Ni foam substrate with a high massloading via a CV electrodeposition route for supercapacitor application[J].Electrochimica Acta,2014,136:189. 44 Sun Yaru, Zhang Weiwei, Li Haiquan, et al. Preparation of graphite-MnO2 composite electrode by cyclic voltammetry and its characteristics analysis[J].Materials Protection,2016,6(7):20(in Chinese). 孙雅茹,张微微,李海全,等.循环伏安法制备石墨-MnO2复合电极及其特性分析[J].材料保护,2016,6(7):20. 45 Huang Wenxin, Li Jun, Xu Yunhe. Nucleation/growth mechanisms and morphological evolution of porous MnO2 coating deposited on graphite for supercapacitor[J].Materials,2017,10(10):1205. 46 Wang Guiling, Wang Wei, Zhao Yufeng, et al. Pulsed electrodeposition of mesoporous cobalt-doped manganese dioxide as supercapacitor electrode material[J].Ionics,2014,20(2):243. 47 Dubal D P, Lokhande C D. Significant improvement in the electrochemicall performancesof nano-nest like amorphous MnO2 electrodes due to Fe doping[J].Ceramics International,2013,39:415. 48 Hua Zhimi, Xiao Xu, Chen Chi, et al. Al-doped α-MnO2 for highmass-loading pseudocapacitor with excellent cycling stability[J].Nano Energy,2015,11:226. 49 Zhang Yong, Yao Qianqian, Gao Haili, et al. Facile synthesis and electrochemical performance of manganese dioxide doped by activated carbon, carbon nanofiber and carbon nanotube[J].Powder Technology,2014,262:150. 50 Liu Tingting, Shao Guangjie, Ji Mingtong, et al. Synthesis of MnO2-graphene composites with enhanced supercapacitive perfor-mance via pulse electrodeposition under supergravity field[J].Journal of Solid State Chemistry,2015,2014:160. 51 Xu Defang, Song Yan, Tian Xiaodong, et al. Preparation and electrochemical properties of nanostructured MnO2/exfoliated graphite composites[J].New Carbon Materials,2016,31(6):615(in Chinese). 徐德芳,宋燕,田晓冬,等.纳米MnO2/膨胀石墨复合材料的制备及其电化学性能[J].新型炭材料,2016,31(6):615. 52 Wang Jiangan, Yang Ying, Huang Zhenghong, et al. MnO2/polypyrrole nanotubular composites: Reactive templatesynthesis, cha-racterization and application as superior electrodematerials for high-performance supercapacitors[J].Electrochimica Acta,2014,130:642. 53 Liu Qin, Cheng Cunxi, Wu Pingping. Preparation of PANI/MnO2 and its application in supercapacitors[J].Guangzhou Chemical Industry,2017,45(16):69(in Chinese). 刘琴,程存喜,吴平平.PANI/MnO2电极的制备及其在超级电容器中的应用[J].广州化工,2017,45(16):69. 54 Zhou Haiyan, Yan Zhe, Yang Xing, et al. RGO/MnO2/polypyrrole ternary film electrode for supercapacitor[J].Materials Chemistry and Physics,2016,177:40. 55 Zhang Lei, Li Tiehu, Ji Xianglin, et al. Freestanding three-dimensional reduced graphene oxide/MnO2 on porous carbon/nickel foam as a designed hierarchical multihole supercapacitor electrode[J].Electrochimica Acta,2017,252:306. 56 Wang Yuqiao, Wang Shasha, Wu Yijun, et al. Polyhedron-core/double-shell CuO@C@MnO2 decorated nickel foam for high performance all-solid-state supercapacitors[J].Electrochimica Acta,2017,246:1065. 57 Lang X, Hirata A, Fujita T, et al. Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors[J].Nature Nanotech-nology,2011,6:232. 58 Liu J, Jiang J, Bosman M, et al. Three-dimensional tubular arrays of MnO2-NiO nanoflakes with high areal pseudocapacitance[J].Journal of Materials Chemistry,2012,22:2419. 59 Sarkar D, Khan G G, Singh A K, et al. High-performance pseudocapacitor electrodes based on a-Fe2O3/MnO2 core-shell nanowire he-terostructure arrays[J].Journal of Physical Chemistry C,2013,117:15523. 60 Su Z, Yang C, Xu C, et al. Co-electro-deposition of the MnO2-PEDOT∶PSS nanostructured composite for high areal mass, flexible asymmetric supercapacitor devices[J].Journal of Materials Chemistry A,2013,1:12432. 61 Ye K H, Liu Z Q, Xu C W, et al. MnO2/reduced graphene oxide composite as high-performance electrode for flexible supercapacitors[J].Inorganic Chemistry Communications,2013,30:1. 62 Li P, Yang Y, Shi E, et al. Core-double-shell, CNT@polypyrrole@MnO2 sponge as freestanding, compressible supercapacitor electrode[J].ACS Applied Materials & Interfaces,2014,6:5228. 63 Kim M, Hwang Y, Kim J. Fabrication of graphene-carbon nanotube papers decorated with manganese oxide nanoneedles on the graphene sheets for supercapacitors[J].Physical Chemistry Chemical Physics,2014,16:351. 64 Wu Wen. Study of metal oxide supercapacitors[D].Shanghai: Fudan University,2010(in Chinese). 吴雯.金属氧化物超级电容器的研究[D].上海:复旦大学,2010. 65 Cui Lihua, Wang Yan, Shu Xia, et al. Preparation and supercapacitive performance of MnO2/TiO2 composite electrodes[J].Acta Materiae Compositae Sinica,2016,33(8):1794(in Chinese). 崔丽华,王岩,舒霞,等.MnO2/TiO2复合物电极的制备及超级电容性能[J].复合材料学报,2016,33(8):1794. 66 Sumboja A, Foo C Y, Wang X, et al. Large areal mass, flexible and free-standing reduced graphene oxide/manganese dioxide paper for asymmetric supercapacitor device[J].Advanced Materials,2013,25:2809. 67 Du Shuangshuang, He Ying, Xu Chenhui, et al. Controllable synthesis of MnO2-PANI composite on carbon cloth and its asymmetric supercapacitor[J].Journal of Functional Polymers,2015(4):353(in Chinese). 杜双双,何颖,徐晨辉,等.碳布负载的MnO2-PANI复合材料的控制合成及其不对称超级电容器[J].功能高分子学报,2015(4):353.
渝公网安备50019002502923号 版权所有：《材料导报》编辑部
2018, Vol. 32 
