Preparation and pseudocapacitance properties of highly conductive sandwich-shaped MnO2/CNTs/MnO2 mesoporous materials

CHEN Zhiyuan1 YAN Dong1 QIAN Fan1 LI Wencui1

(1.School of Chemical Engineering, Dalian University of Technology, Dalian, Liaoning, China 116024)

【Abstract】MnO2 is regarded as the most attractive electrode material for supercapacitor (SC) because of its low cost, non-toxic nature, high natural abundance, and superb theoretical specific capacitance. The tantalum capacitor electrode material MnO2 still has problems of poor conductivity and easy peeling during charging and discharging. In this study, a sandwich MnO2/CNTs/MnO2 mesoporous composite is fabricated by a facile galvanostatic electrochemical deposition approach on the surface of carbon paper pre-oxidized by nitric acid, and the middle layer of carbon nanotubes (CNTs) was added by a simple smear-drying method. The crystal structure, surface morphology, and pore characteristics of the sandwich composite are characterized by means of X-ray diffraction, scanning electron microscopy, and nitrogen adsorption test. The prepared composite shows a sandwich structure with mesopores of about 5 nm, which could ensure the efficient diffusion of electrolyte ions. Three-dimensional carbon paper could provide abundant conductive sites for attachment of MnO2. The synthesized α-MnO2 has a fluffy and porous morphology, which could reduce the expansion stress of the composite effectively. The intermediate layer of CNTs serves as conductive media relay between the inner and outer layers of MnO2 to further improve the conductivity of composite. The composite exhibits excellent electrochemical performance: the electrode has a reversible specific capacity of 428.8 F·g−1 at a current density of 0.1 A·g−1 and an outstanding specific capacitance retention of ca. 80% at 5 A·g−1. Moreover, the electrode still has an excellent cycle stability (95% retention rate) at a current density of 1 A·g−1 after 6 000 cycles.

【Keywords】 manganese dioxide; carbon nanotube; sandwich structure; composites; diffusion; electrochemical; supercapacitor;


【Funds】 National Natural Science Foundation of China (21776041)

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    [1] Ye X G, Zhang X G, Mi H Y, et al. Hydrothermal microemulsion synthesis of Co3O4 with different morphologies and their electrochemical capacitance [J]. Acta Physico-Chimica Sinica, 2008, 24 (6): 1105–1110 (in Chinese).

    [2] Xing B L, Huang G X, Chen L J, et al. Current situation and prospect of research on electrode materials for supercapacitor [J]. Materials Review, 2012, 26 (19): 21–25 (in Chinese).

    [3] Guo Y G, Hu J S, Wan L J. Nanostructured materials for electrochemical energy conversion and storage devices [J]. Advanced Materials, 2008, 20 (15): 2878–2887.

    [4] Liu C, Yu Z, Neff D, et al. Graphene-based supercapacitor with an ultrahigh energy density [J]. Nano Letters, 2010, 10 (12): 4863–4868.

    [5] Wang K, Wu H, Meng Y, et al. Conducting polymer nanowire arrays for high performance supercapacitors [J]. Small, 2014, 10 (1): 14–31.

    [6] Yang P, Ding Y, Lin Z, et al. Low-cost high-performance solid-state asymmetric supercapacitors based on MnO2 nanowires and Fe2O3 nanotubes [J]. Nano Letters, 2014, 14 (2): 731–736.

    [7] Chen W C, Hu C C, Wang C C, et al. Electrochemical characterization of activated carbon–ruthenium oxide nanoparticles composites for supercapacitors [J]. Journal of Power Sources, 2004, 125 (2): 292–298.

    [8] Prasad K R, Miura N. Electrochemically synthesized MnO2-based mixed oxides for high performance redox supercapacitors [J]. Electrochemistry Communications, 2004, 6 (10): 1004–1008.

    [9] Li S H, Liu Q H, Qi L, et al. Progress in research on manganese dioxide electrode materials for electrochemical capacitors [J]. Chinese Journal of Analytical Chemistry, 2012, 40 (3): 339–346.

    [10] Yun Y S, Kim J M, Park H H, et al. Free-standing heterogeneous hybrid papers based on mesoporous γ-MnO2 particles and carbon nano tubes for lithium-ion battery anodes [J]. Journal of Power Sources, 2013, 244: 747–751.

    [11] Ju J, Zhao H, Kang W, et al. Designing MnO2 & carbon composite porous nanofiber structure for supercapacitor applications [J]. Electrochimica Acta, 2017, 258: 116–123.

    [12] Ren Y, Xu Q, Zhang J, et al. Functionalization of biomass carbonaceous aerogels: selective preparation of MnO2@CA composites for supercapacitors [J]. ACS Applied Materials & Interfaces, 2014, 6 (12): 9689–9697.

    [13] Yuan A, Zhang Q. A novel hybrid manganese dioxide/activated carbon supercapacitor using lithium hydroxide electrolyte [J]. Electrochemistry Communications, 2006, 8 (7): 1173–1178.

    [14] Hu L, Chen W, Xie X, et al. Symmetrical MnO2–carbon nanotube textile nanostructures for wearable pseudocapacitors with high mass loading [J]. ACS Nano, 2011, 5 (11): 8904–8913.

    [15] Xu P, Wei B, Cao Z, et al. Stretchable wire-shaped asymmetric supercapacitors based on pristine and MnO2 coated carbon nanotube fibers [J]. ACS Nano, 2015, 9 (6): 6088–6096.

    [16] Li L, Hu Z A, An N, et al. Facile synthesis of MnO2/CNTs composite for supercapacitor electrodes with long cycle stability [J]. The Journal of Physical Chemistry C, 2014, 118 (40): 22865–22872.

    [17] Li P, Yang Y, Shi E, et al. Core-double-shell, carbon nanotube@polypyrrole@MnO2 sponge as freestanding, compressible supercapacitor electrode [J]. ACS Applied Materials & Interfaces, 2014, 6 (7): 5228–5234.

    [18] Yan J, Fan Z, Wei T, et al. Fast and reversible surface redox reaction of graphene–MnO2 composites as supercapacitor electrodes [J]. Carbon, 2010, 48 (13): 3825–3833.

    [19] Yu G, Hu L, Vosgueritchian M, et al. Solution-processed graphene/MnO2 nanostructured textiles for high-performance electrochemical capacitors [J]. Nano Letters, 2011, 11 (7): 2905–2911.

    [20] Wang G, Tang Q, Bao H, et al. Synthesis of hierarchical sulfonated graphene/MnO2/polyaniline ternary composite and its improved electrochemical performance [J]. Journal of Power Sources, 2013, 241: 231–238.

    [21] He Y, Chen W, Li X, et al. Freestanding three-dimensional graphene/MnO2 composite networks as ultralight and flexible supercapacitor electrodes [J]. ACS Nano, 2012, 7 (1): 174–182.

    [22] Ma J, Cheng Q, Pavlinek V, et al. Morphology-controllable synthesis of MnO2 hollow nanospheres and their supercapacitive performance [J]. New Journal of Chemistry, 2013, 37 (3): 722–728.

    [23] Giovambattista N, Debenedetti P G, Rossky P J. Effect of surface polarity on water contact angle and interfacial hydration structure [J]. The Journal of Physical Chemistry B, 2007, 111 (32): 9581–9587.

    [24] Wu Z S, Wang D W, Ren W, et al. Anchoring hydrous RuO2 on graphene sheets for high-performance electrochemical capacitors [J]. Advanced Functional Materials, 2010, 20 (20): 3595–3602.

    [25] W alcarius A. Mesoporous materials and electrochemistry [J]. Chemical Society Reviews, 2013, 42 (9): 4098–4140.

    [26] Wan C, Shen H, Ye X, et al. Facial synthesis of 3D MnO2 nanofibers sponge and its application in supercapacitors [J]. International Journal of Electrochemical Science, 2018, 13 (12): 12320–12330.

    [27] Li H, Wang W, Pan F, et al. Synthesis of single-crystalline α-MnO2 nanotubes and structural characterization by HRTEM [J]. Materials Science and Engineering: B, 2011, 176 (14): 1054–1057.

    [28] Zhang L, Li T, Ji X, 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: 306–314.

    [29] Lee H Y, Goodenough J B. Supercapacitor behavior with KCl electrolyte [J]. Journal of Solid State Chemistry, 1999, 144 (1): 220–223.

    [30] Zhao L, Fan L Z, Zhou M Q, et al. Nitrogen-containing hydrothermal carbons with superior performance in supercapacitors [J]. Advanced Materials, 2010, 22 (45): 5202–5206.

    [31] Hsieh C T, Chen W Y, Cheng Y S. Influence of oxidation level on capacitance of electrochemical capacitors fabricated with carbon nanotube/carbon paper composites [J]. Electrochimica Acta, 2010, 55 (19): 5294–5300.

    [32] Feng X, Yan Z, Chen N, et al. The synthesis of shape-controlled MnO2/graphene composites via a facile one-step hydrothermal method and their application in supercapacitors [J]. Journal of Materials Chemistry A, 2013, 1 (41): 12818–12825.

This Article


CN: 11-1946/TQ

Vol 70, No. 12, Pages 4864-4871

December 2019


Article Outline


  • Introduction
  • 1 Experimental materials and methods
  • 2 Experimental results and discussion
  • 3 Conclusion
  • Symbols
  • References