基于二氧化锰/石墨烯复合材料的制备方法及在超级电容器上的研究进展

doi:10.12028/j.issn.2095-4239.2018.0220

摘要/Abstract

摘要： 综述了基于MnO₂/石墨烯的二元、三元复合材料在超级电容器方面的最新研究进展。由于范德华力造成的堆叠，石墨烯实际比电容并不高。MnO₂理论比电容高达1370 F/g，但因其赝电容受MnO₂片层厚度的限制，实际比电容远小于理论值。将石墨烯和MnO₂复合，MnO₂纳米结构锚定在石墨烯纳米片之间充当间隔物，可以有效抑制石墨烯的堆叠，增强界面电荷转移，借助二者的协同效应有望实现高比电容、高电导率和良好的循环稳定性。介绍了MnO₂/石墨烯复合材料的制备方法及电化学性能。对比分析了MnO₂/石墨烯三元复合材料的电化学性能，由于金属氧化物或导电聚合物的引入，电化学性能进一步提升。最后总结指出基于MnO₂/石墨烯的多元复合材料和器件还面临着安全可靠、规模化生产以及降成本等一系列问题。随着技术的不断成熟和突破，有望在工业、交通以及日常电子器件中获得应用。

关键词: 石墨烯, 二氧化锰, 复合材料, 超级电容器

Abstract: The latest research progress of MnO₂/graphene based binary and ternary composites in supercapacitors are reviewed. Due to the stacking caused by van der Waals forces, the actual specific capacitance of graphene is not very high. The theoretical specific capacitance of MnO₂ is as high as 1370 F/g, but its pseudo capacitance is limited by the thickness of MnO₂, and the actual specific capacitance is much smaller than the theoretical value. The combination of graphene and MnO₂, where MnO₂ nanostructures anchored between graphene nanosheets as spacers, can effectively inhibit the stacking of graphene and enhance the interface charge transfer. With the synergistic effect of both functions, it is expected to achieve high specific capacitance and high conductivity and good cycling stability. The preparation method and electrochemical performance of MnO₂/graphene composites are introduced. The electrochemical performance of MnO₂/graphene ternary composites are analyzed. The introduction of metal oxides or conductive polymers can further improve the electrochemical performance. Finally, a series of issues for the application of MnO₂/graphene-based multi-component composites and devices are analyzed, such as safety and reliability, large-scale production and cost reduction. With the mature and break-through of technology, it is expected to achieve applications in industry, transportation and daily electronics.

Key words: graphene, manganese dioxide, composites, supercapacitors

中图分类号:

TB34

李伟, 侯朝霞, 李建君, 薄大明. 基于二氧化锰/石墨烯复合材料的制备方法及在超级电容器上的研究进展[J]. 储能科学与技术, 2019, 8(2): 248-259.

LI Wei, HOU Zhaoxia, LI Jianjun, BO Daming. Preparation methods and progress of manganese dioxide/graphene based composites in supercapacitors[J]. Energy Storage Science and Technology, 2019, 8(2): 248-259.

参考文献

[1] WANG K, WU H P, MENG Y N, et al. Conducting polymer nanowire arrays for high performance supercapacitors[J]. Small, 2014, 10(1):14-31.
[2] LIU W W, LI X, ZHU M H, et al. High-performance all-solid state asymmetric supercapacitor based on Co₃O₄ nanowires and carbon aerogel[J]. Journal of Power Sources, 2015, 282:179-186.
[3] WANG Q H, JIAO L F, DU H M, et al. Fe₃O₄ nanoparticles grown on graphene as advanced electrode materials for supercapacitors[J]. Journal of Power Sources, 2014, 245:101-106.
[4] MA W J, CHEN S H, YANG S Y, et al. Hierarchical MnO₂ nanowire/graphene hybrid fibers with excellent electrochemical performance for flexible solid-state supercapacitors[J]. Journal of Power Sources, 2016, 306:481-488.
[5] ZHANG Y B, DING M J, SONG C J, et al. Selective catalytic reduction of NO with NH₃ over MnO₂/PDOPA@CNT catalysts prepared by poly(dopamine) functionalization[J]. New Journal of Chemistry, 2018, 42(14):11273-11275.
[6] LI X, DONG F, XU N, et al. Co₃O₄/MnO₂/hierarchically porous carbon as superior bifunctional electrodes for liquid and all-solid-state rechargeable zinc-air batteries[J]. ACS Appl. Mater. Interfaces, 2018, 10(18):15591-15601.
[7] YAO B, ZHANG J, KOU T Y, et al. Paper-based electrodes for flexible energy storage devices[J]. Advanced Science, 2017, 4(7):doi:10.1002/advs.201700107.
[8] HUI N, CHAI F L, LIN P P, et al. Electrodeposited conducting polyaniline nanowire arrays aligned on carbon nanotubes network for high performance supercapacitors and sensors[J]. Electrochim. Acta, 2016, 199:234-241.
[9] GARAKANI M A, ABOUALI S, CUI J, et al. In-situ TEM study of lithiation into PPy coated α-MnO₂/graphene foam freestanding electrode[J]. Materials Chemistry Frontiers, 2018, 2(8):1481-1488.
[10] IGUCHI H, MIYAHARA K, HIGASHI C, et al. Preparation of uncurled and planar multilayered graphene using polythiophene derivatives via liquid-phase exfoliation of graphite[J]. FlatChem, 2018, 8:31-39.
[11] BAG S, RETNA RAJ C. Hierarchical three-dimensional mesoporous MnO₂ nanostructures for high performance aqueous asymmetric supercapacitors[J]. Mater. Chem., 2016, 4(2):587-595.
[12] WANG K, YANG J, ZHU J, et al. General solution-processed formation of porous transition-metal oxides on exfoliated molybdenum disulfides for high-performance asymmetric supercapacitors[J]. Journal of Materials Chemistry A, 2017, 5(22):11236-11245.
[13] RAMESH S, KARUPPASAMY K, MSOLLI S, et al. Nanocrystalline structured of NiO/MnO₂@nitrogen-doped graphene oxide hybrid nanocomposite for high performance supercapacitor[J]. New Journal of Chemistry, 2017, 41(24):15517-15527.
[14] ZHANG Q Z, ZHANG D, MIAO Z C, et al. Research progress in MnO₂-carbon based supercapacitor electrode materials[J]. Small, 2018, 14(24):doi:10.1002/smll.201702883.
[15] SUN S Q, JIANG G H, LIU Y K, et al. Facile preparation of hybrid films based on MnO₂ and reduced graphene oxide for a flexible supercapacitor[J]. Journal of Electronic Materials, 2018, 47(10):5993-5999.
[16] GAO G, ZHANG Q, CHENG X B, et al. Synthesis of three-dimensional rare-earth ions doped CNTs-GO-Fe₃O₄ hybrid structures using one-pot hydrothermal method[J]. Journal of Alloys & Compounds, 2015, 649:82-88.
[17] SUN H B, GU H Z, CHEN Y. Preparation and electrochemical properties of graphene/MnO₂ nanocomposites for supercapacitors[J]. Key Engineering Materials, 2018, 768:102-108.
[18] ZHANG L F, DU S Q, LIU Y, et al. Manganese dioxide nanoflakes anchored on reduced graphene oxide with superior electrochemical performance for supercapacitorss[J]. IET Micro & Nano Letters, 2017, 12(3):147-150.
[19] MENG X Y, LU L, SUN C W. Green synthesis of three-dimensional MnO₂/graphene hydrogel composites as a high-performance electrode material for supercapacitors[J]. Mater. Interfaces, 2018, 10(19):16474-16481.
[20] ZHAO X, WANG H, ZHAI G, et al. Facile assembly of 3D porous reduced graphene oxide/ultrathin MnO₂ nanosheets-S aerogels as efficient polysulfide adsorption sites for high-performance lithium-sulfur batteries[J]. Chemistry, 2017, 23(29):7037-7045.
[21] XU J, CHEN Y, DONG Z, et al. Facile synthesis of the Ti³⁺-TiO₂-RGO compound with controllable visible light photocatalytic performance:GO regulating lattice defects[J]. Journal of Materials Science, 2018, 53(18):12770-12780.
[22] LIU C L, GUI D Y, LIU J H. Process dependent graphene-wrapped plate-like MnO₂ nanospheres for high performance supercapacitor[J]. Chemical Physics Letters, 2014, 614:123-128.
[23] ZHAO X, TANG J, YU F, et al. Preparation of graphene nanoplatelets reinforcing copper matrix composites by electrochemical deposition[J]. Journal of Alloys and Compounds, 2018, 766(25):266-273.
[24] XIONG C Y, LI T H, ZHAO T K, et al. Three-dimensional graphene/MnO₂ nanowalls hybrid for high-efficiency electrochemical supercapacitors[J]. NANO, 2018, 13(1):doi:10.1142/s1793292018500133.
[25] ZHOU J H, CHEN N N, GE Y, et al. Flexible all-solid-state micro-supercapacitor based on Ni fiber electrode coated with MnO₂ and reduced graphene oxide via electrochemical deposition[J]. Science China Materials, 2018, 6(12):243-253.
[26] FALCAO E H L, BLAIR R G, MACK J J, et al. Microwave exfoliation of a graphite intercalation compound[J]. Carbon, 2007, 45(6):1367-1369.
[27] VIMUNA V M, ATHIRA A R, XAVIER T S, et al. Microwave assisted synthesis of graphene oxide-MnO₂ nanocomposites for electrochemical supercapacitors[J]. AIP Conference Proceedings, 2018, 1953(1):doi:10.1063/1.5032471.
[28] YAN J, FAN Z J, WEI T, et al. Fast and reversible surface redox reaction of graphene-MnO₂ composites as supercapacitor electrodes[J]. Carbon, 2010, 48(13):3825-3833.
[29] LIU R R, WEN D D, ZHANG X Y, et al. Three-dimensional reduced-graphene/MnO₂ prepared by plasma treatment as high-performance supercapacitor electrodes[J]. Materials Research Express, 2018, 5(6):doi:10.1088/2053-1591/aac7b4.
[30] QIU X, XU D Y, MA L, et al. Preparation of manganese oxide/graphene aerogel and its application as an advanced supercapacitor electrode material[J]. International Journal of Electrochemical Science, 2017, 12:2173-2183.
[31] ZHAO Y F, RAN W, HE J, et al. High-performance asymmetric supercapacitor based on multilayer MnO₂/graphene oxide nanoflakes and hierarchical porous carbon with enhanced cycling stability[J]. Small, 2014, 11(11):1310-1319.
[32] MA W J, CHEN S H, YANG S Y, et al. Flexible all-solid-state asymmetric supercapacitor based on transition metal oxide nanorods/reduced graphene oxide hybrid fibers with high energy density[J]. Carbon, 2017, 113:151-158.
[33] SHENG L Z, JIANG L L, WEI T, et al. Fe(CN)₆^3- ion-modified MnO₂/graphene nanoribbons enabling high energy density asymmetric supercapacitors[J]. Journal of Materials Chemistry A, 2018, 6(17):7649-7658.
[34] RAKHI R B, ALHEBSHI N A, ANJUM D H, et al. Nanostructured cobalt sulfide-on-fiber with tunable morphology as electrodes for asymmetric hybrid supercapacitors[J]. Journal of Materials Chemistry A, 2014, 2(38):16190-16198.
[35] LI J, CHEN Y, WU Q, et al. Synthesis and electrochemical properties of Fe₃O₄/MnO₂/RGOs sandwich-like nano-superstructures[J]. Journal of Alloys & Compounds, 2017, 693:373-380.
[36] OJHA G P, PANT B, PARK S J, et al. Synthesis and characterization of reduced graphene oxide decorated with CeO₂-doped MnO₂ nanorods for supercapacitor applications[J]. Journal of Colloid & Interface Science, 2017, 494:338-344.
[37] WANG K, LI L W, XUE W, et al. Electrodeposition synthesis of PANI/MnO₂/graphene composite materials and its electrochemical performance[J]. International Journal of Electrochemical Science, 2017, 12(9):8306-8314.
[38] JI J Y, ZHANG X Y, HUANG Z L, et al. One-step synthesis of graphene oxide/polypyrrole/MnO₂ ternary nanocomposites with an improved electrochemical capacitance[J]. Journal of Nanoscience & Nanotechnology, 2017, 17(6):4356-4361.
[39] 刘文杰, 孙现众, 郝青丽. 电化学沉积制备MnO₂/PEDOT:PSS复合材料及其电容特性研究[J]. 储能科学与技术, 2018, 7(2):262-269. LIU W J, SUN X Z, HAO Q L. Electrochemical deposition of MnO₂/PEDOT:PSS composite and its capacitance characteristics[J]. Energy Storage Science and Technology, 2018, 7(2):262-269.
[40] HAREESH K, SHATEESH B, JOSHI R P, et al. Ultra high stable supercapacitance performance of conducting polymer coated MnO₂ nanorods/RGO nanocomposites[J]. RSC Advances, 2017, 7(32):20027-20036.
[41] WU T, WANG C N, MO Y, et al. A ternary composite with manganese dioxide nanorods and graphene nanoribbons embedded in a polyaniline matrix for high-performance supercapacitors[J]. RSC Advances, 2017, 7(53):33591-33599.