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Nano Research 2011, 4(2): 216-225 https://doi.org/10.1007/s12274-010-0072-y
Research Article | Open Access | Issue | Published: 01 February 2011

Hierarchical Manganese Oxide/Carbon Nanocomposites for Supercapacitor Electrodes

Show Author's Information Yiting Peng1,2,§,  Zheng Chen2,§,  Jing Wen2,  Qiangfeng Xiao2,  Ding Weng2,  Shiyu He1( ),  Hongbin Geng1( ),  Yunfeng Lu2( )
Department of Materials Science and EngineeringHarbin Institute of TechnologyHarbin150001China
Department of Chemical and Biomolecular EngineeringUniversity of CaliforniaLos AngelesCA90095USA

§ These authors contributed equally.

Keywords:
supercapacitor, Hierarchically porous carbon, MnO2/carbon nanocomposite
Cite this article:
Peng Y, Chen Z, Wen J, et al. Hierarchical Manganese Oxide/Carbon Nanocomposites for Supercapacitor Electrodes. Nano Research, 2011, 4(2): 216-225. https://doi.org/10.1007/s12274-010-0072-y
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Abstract Full text Electronic supplementary material About this article

MnO2/carbon nanocomposites with hierarchical pore structure and controllable MnO2 loading have been synthesized using a self-limiting growth method. This was achieved by the redox reactions of KMnO4 with sacrificed carbon substrates that contain hierarchical pores. The unique pore structure allows the synthesis of nanocomposites with tunable MnO2 loading up to 83 wt.%. The specific capacitance of the nanocomposites increased with the MnO2 loading; the conductivity measured by electrochemical impedance spectroscopy, on the other hand, decreased with increasing MnO2 loading. Optimization of the MnO2 loading resulted in nanocomposites with high specific capacitance and excellent rate capability. This work provides important fundamental understanding which will facilitate the design and fabrication of high-performance supercapacitor materials for a large variety of applications.


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Electronic supplementary material
About this article

Hierarchical Manganese Oxide/Carbon Nanocomposites for Supercapacitor Electrodes

Show Author's information Yiting Peng1,2,§, Zheng Chen2,§, Jing Wen2, Qiangfeng Xiao2, Ding Weng2, Shiyu He1( ), Hongbin Geng1( ), Yunfeng Lu2( )
Department of Materials Science and EngineeringHarbin Institute of TechnologyHarbin150001China
Department of Chemical and Biomolecular EngineeringUniversity of CaliforniaLos AngelesCA90095USA

§ These authors contributed equally.

Abstract

MnO2/carbon nanocomposites with hierarchical pore structure and controllable MnO2 loading have been synthesized using a self-limiting growth method. This was achieved by the redox reactions of KMnO4 with sacrificed carbon substrates that contain hierarchical pores. The unique pore structure allows the synthesis of nanocomposites with tunable MnO2 loading up to 83 wt.%. The specific capacitance of the nanocomposites increased with the MnO2 loading; the conductivity measured by electrochemical impedance spectroscopy, on the other hand, decreased with increasing MnO2 loading. Optimization of the MnO2 loading resulted in nanocomposites with high specific capacitance and excellent rate capability. This work provides important fundamental understanding which will facilitate the design and fabrication of high-performance supercapacitor materials for a large variety of applications.

Keywords: supercapacitor, Hierarchically porous carbon, MnO2/carbon nanocomposite

References(52)

1

Kötz, R.; Carlen, M. Principles and applications of electrochemical capacitors. Electrochim. Acta. 2000, 45, 2483–2498.
DOI Google Scholar
2

Conway, B. E. Electrochemical supercapacitors: Scientific fundamentals and technological applications; Kluwer Academic/Plenum: New York, 1999.
3

Huggins, R. A.; Parsons, R. Supercapacitors. Phil. Trans. R. Soc. Lond. A. 1996, 354, 1555–1566.
DOI Google Scholar
4

Liu, H.; Mao, C.; Lu, J.; Wang, D. Electronic power transformer with supercapacitors storage energy system. Electr. Pow. Syst. Res. 2009, 79, 1200–1208.
DOI Google Scholar
5

Raymundo-Pińero, E.; Cadek, M.; Béguin, F. Tuning carbon materials for supercapacitors by direct pyrolysis of seaweeds. Adv. Funct. Mater. 2009, 19, 1032–1039.
DOI Google Scholar
6

Arico, A. S.; Bruce, P.; Scrosati, B.; Tarascon, J. M.; van Schalkwijk, W. Nanostructured materials for advanced energy conversion and storage devices. Nat. Mater. 2005, 4, 366.
DOI Google Scholar
7

Chmiola, J.; Yushin, G.; Gogotsi, Y.; Portet, C.; Simon, P.; Taberna, P. L. Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer. Science 2006, 313, 1760–1763.
DOI Google Scholar
8

Centeno, T. A.; Stoeckli, F. On the specific double-layer capacitance of activated carbons, in relation to their structural and chemical properties. J. Power Sources. 2006, 154, 314–320.
DOI Google Scholar
9

Frackowiak, E. Carbon materials for supercapacitor application. Phys. Chem. Chem. Phys. 2007, 9, 1774–1785.
DOI Google Scholar
10

Zheng, J. P.; Cygan, P. J.; Jow, T. R. Hydrous ruthenium oxide as an electrode material for electrochemical capacitors. J. Electrochem. Soc. 1995, 142, 2699–2703.
DOI Google Scholar
11

Subramanian, V.; Hall, S. C.; Smith, P. H.; Rambabu, B. Mesoporous anhydrous RuO2 as a supercapacitor electrode material. Solid State Ionics. 2004, 175, 511–515.
DOI Google Scholar
12

Wang, Y. G.; Wang, Z. D.; Xia, Y. Y. An asymmetric supercapacitor using RuO2/TiO2 nanotube composite and activated carbon electrodes. Electrochim. Acta. 2005, 50, 5641–5646.
DOI Google Scholar
13

Toupin, M.; Brousse, T.; Belanger, D. Influence of micro-stucture on the charge storage properties of chemically synthesized manganese dioxide. Chem. Mater. 2002, 14, 3946–3952.
DOI Google Scholar
14

Pang, S. C.; Anderson, M. A.; Chapman, T. W. Novel electrode materials for thin-film ultracapacitors: Comparison of electrochemical properties of sol-gel-derived and electro-deposited manganese dioxide. J. Electrochem. Soc. 2000, 147, 444–450.
DOI Google Scholar
15

Chang, J.; Lee, S.; Ganesh, T.; Mane, R. S.; Min, S.; Lee, W.; Han, S. H. Viologen-assisted manganese oxide electrode for improved electrochemical supercapacitors. J. Electroanal. Chem. 2008, 624, 167–173.
DOI Google Scholar
16

Subramanian, V.; Zhu, H.; Wei, B. Nanostructured MnO2: Hydrothermal synthesis and electrochemical properties as a supercapacitor electrode material. J. Power Sources. 2006, 159, 361–364.
DOI Google Scholar
17

Liu, K. C.; Anderson, M. A. Porous nickel oxide/nickel films for electrochemical capacitors. J. Electrochem. Soc. 1996, 143, 124–130.
DOI Google Scholar
18

Lang, J. W.; Kong, L. B.; Wu, W. J.; Luo, Y. C.; Kang, L. Synthesis, characterization, and electrochemical properties of Ni(OH)2/ultra-stable Y zeolite composite. J. Mater. Sci. 2009, 44, 4466–4471.
DOI Google Scholar
19

Lin, C.; Ritter, J. A.; Popov, B. N. Characterization of sol-gel-derived cobalt oxide xerogels as electrochemical capacitors. J. Electrochem. Soc. 1998, 145, 4097–4103.
DOI Google Scholar
20

Reddy, R. N.; Reddy, R. G. Porous structured vanadium oxide electrode material for electrochemical capacitors. J. Power Sources. 2006, 156, 700–704.
DOI Google Scholar
21

Hu, C. C.; Huang, C. M.; Chang, K. H. Anodic deposition of porous vanadium oxide network with high power characteristics for pseudocapacitors. J. Power Sources. 2008, 185, 1594–1597.
DOI Google Scholar
22

Sato, Y.; Yomogida, K.; Nanaumi, T.; Kobayakawa, K.; Ohsawa, Y.; Kawai, M. Electrochemical behavior of activated-carbon capacitor materials loaded with ruthenium oxide. Electrochem. Solid-State Lett. 2000, 3, 113–116.
DOI Google Scholar
23

Kim, I. H.; Kim, J. H.; Lee, Y. H.; Kim, K. B. Synthesis and characterization of electrochemically prepared ruthenium oxide on carbon nanotube film substrate for supercapacitor applications. J. Electrochem. Soc. 2005, 152, A2170–A2178.
DOI Google Scholar
24

Chen, Z.; Qin, Y.; Weng, D.; Xiao, Q.; Peng, Y.; Wang, X.; Li, H.; Wei, F.; Lu, Y. Design and synthesis of hierarchical nanowire composites for electrochemical energy storage. Adv. Funct. Mater. 2009, 19, 3420–3426.
DOI Google Scholar
25

Wu, M.; Snook, G. A.; Chen, G. Z.; Fray, D. Redox deposition of manganese oxide on graphite for supercapacitors. J. Electrochem. Commun. 2004, 6, 499–504.
DOI Google Scholar
26

Huang, X.; Yue, H.; Attia, A.; Yang, Y. Preparation and properties of manganese oxide/carbon composites by reduction of potassium permanganate with acetylene black. J. Electrochem. Soc. 2007, 154, A26.
DOI Google Scholar
27

Ma, S. B.; Lee, Y. H.; Ahn, K. Y.; Kim, C. M.; Oh, K. H.; Kim, K. B. Spontaneously deposited manganese oxide on acetylene black in an aqueous potassium permanganate solution. J. Electrochem. Soc. 2006, 153, C27–C32.
DOI Google Scholar
28

Zhu, S.; Zhou, H.; Hibino, M.; Honma, I.; Ichihara, M. Synthesis of MnO2 nanoparticles confined in ordered mesoporous carbon using a sonochemical method. Adv. Funct. Mater. 2005, 15, 381–386.
DOI Google Scholar
29

Dong, X.; Shen, W.; Gu, J.; Xiong, L.; Zhu, Y.; Li, H.; Shi, H. J. MnO2-embedded-in-mesoporous-carbon-wall structure for use as electrochemical capacitors. J. Phys. Chem. B. 2006, 110, 6015–6019.
DOI Google Scholar
30

Zhang, H.; Cao, G.; Wang, Z.; Yang, Y.; Shi, Z.; Gu, Z. Growth of manganese oxide nanoflowers on vertically-aligned carbon nanotube arrays for high-rate electrochemical capacitive energy storage. Nano Lett. 2008, 8, 2664–2668.
DOI Google Scholar
31

Raymundo-Pińero, E.; Khomenko, V.; Frackowiak, E.; Béguin, F. Performance of manganese oxide/CNTs composites as electrode materials for electrochemical capacitors. J. Electrochem. Soc. 2005, 152, A229–A235.
DOI Google Scholar
32

Lee, C. Y.; Tsai, H. M.; Chuang, H. J.; Li, S. Y.; Lin, P.; Tsen, T. Y. Characteristics and electrochemical performance of supercapacitors with manganese oxide-carbon nanotube nanocomposite electrodes. J. Electrochem. Soc. 2005, 152, A716–A720.
DOI Google Scholar
33

Fan, Z.; Chen, J.; Wang, M.; Cui, K.; Zhou, H.; Kuang, Y. Preparation and characterization of manganese oxide/CNT composites as supercapacitive materials. Diam. Relat. Mater. 2006, 15, 1478–1483.
DOI Google Scholar
34

Fischer, A. E.; Pettigrew, K. A.; Rolison, D. R.; Stroud, R. M.; Long, J. W. Incorporation of homogeneous, nanoscale MnO2 within ultraporous carbon structures via self-limiting electroless deposition: Implications for electrochemical capacitors. Nano Lett. 2007, 7, 281–286.
DOI Google Scholar
35

Chu, H. Y.; Lai, Q. Y.; Wang, L.; Lu, J. F.; Zhao, Y. Preparation of MnO2/WMNT composite and MnO2/AB composite by redox deposition method and its comparative study as supercapacitive materials. Ionics. 2009, 16, 233–238.
DOI Google Scholar
36

Wang, D. W.; Li, F.; Liu, M.; Lu, G.; Cheng, H. M. 3D aperiodic hierarchical porous graphitic carbon material for high-rate electrochemical capacitive energy storage. Angew. Chem. Int. Ed. 2008, 47, 373–376.
DOI Google Scholar
37

Jiao, F.; Bruce, P. G. Mesoporous crystalline β-MnO2-reversible positive electrode for rechargeable lithium batteries. Adv. Mater. 2007, 5, 657–660.
DOI Google Scholar
38

Jin, X.; Zhou, Wu.; Zhang, S.; Chen, G. Z. Nanoscale microelectrochemical cells on carbon nanotubes. Small. 2007, 3, 1513–1517.
DOI Google Scholar
39

Meng, Y.; Gu, D.; Zhang, F.; Shi, Y.; Yang, H.; Li, Z.; Yu, C.; Tu, B.; Zhao, D. Ordered mesoporous polymers and homologous carbon frameworks: Amphiphilic surfactant templating and direct transformation. Angew. Chem. Int. Ed. 2005, 44, 7053–7059.
DOI Google Scholar
40

Feng, Q.; Sun, E. H.; Yanagisawa, K.; Yamasaki, N. Synthesis of birnessite-type sodium manganese oxides by solution reaction and hydrothermal methods. J. Ceram. Soc. Jpn. 1997, 105, 564–568.
DOI Google Scholar
41

Shen, B.; Qin, L. Study on MSW catalytic combustion by TGA. Energy Convers. Manage. 2006, 47, 1429–1437.
DOI Google Scholar
42

Liu, L.; Feng, Q.; Yanagisawa, K.; Wang, Y. Characterization of birnessite-type sodium manganese oxides prepared by hydrothermal reaction process. J. Mater. Sci. Lett. 2000, 19, 2047–2050.
DOI Google Scholar
43

Feng, Q.; Yanagisawa, K.; Yamasaki, N. Synthesis of birnessite-type potassium manganese oxide. J. Mater. Sci. Lett. 1997, 16, 110–112.
DOI Google Scholar
44

Sharma, R. K.; Oh, H. S.; Shul, Y. G.; Kim, H. Growth and characterization of carbon-supported MnO2 nanorods for supercapacitor electrode. Phy. Rev. B: Condens. Matter. 2008, 403, 1763–1769.
DOI Google Scholar
45

Liu, R.; Shi, Y.; Wan, Y.; Meng, Y.; Zhang, F.; Gu, D.; Chen, Z.; Tu, B.; Zhao, D. Triconstituent co-assembly to ordered mesostructured polymer−silica and carbon−silica nanocomposites and large-pore mesoporous carbons with high surface areas. J. Am. Chem. Soc. 2006, 128, 11652–11662.
DOI Google Scholar
46

Vol'khin, V. V.; Pogodina, O. A.; Leont'eva, G. V. Nonstoi-chiometric compounds based on manganese(III, IV) oxides with the birnessite structure. Russ. J. Gen. Chem. 2002, 72, 173–177.
DOI Google Scholar
47

Devaraj, S.; Munichandraiah, N. Effect of crystallographic structure of MnO2 on its electrochemical capacitance properties. J. Phys. Chem. C. 2008, 112, 4406–4417.
DOI Google Scholar
48

Luo, J.; Huang, A.; Park, S. H.; Suib, S. L.; O'Young, C. Crystallization of sodium β-birnessite and accompanied phase transformation. Chem. Mater. 1998, 10, 1561–1568.
DOI Google Scholar
49

Hu, Q.; Lu, Y.; Meisner, G. P. Preparation of nanoporous carbon particles and their cryogenic hydrogen storage capacities. J. Phys. Chem. C. 2008, 112, 1516–1523.
DOI Google Scholar
50

Brock, S. L.; Duan, N.; Tian, Z. R.; Giraldo, O.; Zhou, H.; Suib, S. L. A review of porous manganese oxide materials. Chem. Mater. 1998, 10, 2619–2628.
DOI Google Scholar
51

Toupin, M.; Brousse, T.; Belanger, D. Charge storage mechanism of MnO2 electrode used in aqueous electrochemical capacitor. Chem. Mater. 2004, 16, 3184–3190.
DOI Google Scholar
52

Guzman, R. N. D.; Awaluddin, A.; Shen, Y.; Tian, Z.; Suib, S. L.; Ching, S.; O'Young, C. Electrical resistivity measurements on manganese oxides with layer and tunnel structures: Birnessites, todorokites, and cryptomelanes. Chem. Mater. 1995, 7, 1286–1292.
DOI Google Scholar
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Publication history
Copyright
Acknowledgements

Publication history

Received: 14 October 2010
Revised: 05 November 2010
Accepted: 06 November 2010
Published: 01 February 2011
Issue date: February 2011

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2010

Acknowledgements

Acknowledgements

This work was partially supported by the Center for Molecularly Assembled Material Architectures for Solar Energy Production, Storage, and Carbon Capture, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award DE-SC0001342.

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