Abstract
Technological progress is determined to a greater extent by developments of novel materials or new combinations of known materials with different dimensionality and diverse functionality. In this work, we report on the synthesis and characterization of graphene-based hybrid nanomaterials coupled with transition-metal oxide polymorphs (nano/micro-manganese oxides, i.e., β-MnO2 [Mn(IV)] and Mn3O4 [Mn(II, III)]). This lays the groundwork for high-performance electrochemical electrodes for alternative energy devices owing to their higher specific capacitance, wide operational potential window and stability through charge–discharge cycling, environmentally benignity, cost-effectiveness, easy processing, and reproducibility on a larger scale. To accomplish this, we strategically designed these hybrids by direct anchoring or physical adsorption of β-MnO2 and Mn3O4 on variants of graphene, namely graphene oxide and its reduced form, via mixing dispersions of the constituents under mild ultrasonication and drop-casting, resulting in four different combinations. This facile approach affords strong chemical/physical attachment and is expected to result in coupling between the pseudocapacitive transition-metal oxides and supercapacitive nanocarbons showing enhanced activity/reactivity and reasonable areal density of tailored interfaces. We used a range of complementary analytical characterization tools to determine the structure and physical properties, such as scanning electron microscopy combined with energy-dispersive x-ray spectroscopy, atomic force microscopy, x-ray diffraction, resonance Raman spectroscopy combined with elemental Raman mapping, and transmission electron microscopy in conjunction with selected-area electron diffraction. All of these techniques reveal surface morphology, local (lattice dynamical) and average structure, and local charge transfer due to the physically (or chemically) adsorbed manganese oxide of synthesized hybrids that helps to establish microscopic structure–property–function correlations highlighting the surface structure and interfaces to further investigate their electrochemical supercapacitor properties.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
A.K. Geim and K.S. Novoselov, Nat. Mater. 6, 183 (2007).
S. Gupta, E. Heintzman, and J. Jasinski, J. Electron. Mater. July 4 Issue (2014) and references therein.
Y. Zhang, Y.-W. Tan, H.L. Stormer, and P. Kim, Nature 438, 201 (2005).
M.D. Stoller, S. Park, Y. Zhu, J. An, and R.S. Ruoff, Nano Lett. 8, 3498 (2008).
C. Lee, X.D. Wei, J.W. Kysar, and J. Hone, Science 321, 385 (2008).
C. Liu, Z. Yu, D. Neff, A. Zhamu, and B.Z. Jang, Nano Lett. 10, 4863 (2010).
F. Liu, C. W. Lee, S. S. Im, J. Nanomater. 1 (2013).
Y. Hou, M. Shao, B.R. Ellis, and B. Yi, PCCP 13, 15384 (2011).
K.P. Loh, Q.L. Bao, P.K. Ang, and J.X. Yang, J. Mater. Chem. 20, 2277 (2010).
A. Bagri, C. Mattevi, M. Acik, Y.J. Chabal, M. Chowalla, and V.B. Shenoy, Nat. Chem. 2, 581 (2010).
K.P. Loh, Q. Bao, G. Eda, and M. Chowalla, Nat. Chem. 2, 1015 (2014).
G. Eda and M. Chowalla, Adv. Mater. 22, 2392 (2010).
F. Schwierz, Nat. Nanotechnol. 5, 487 (2010).
P. Blake, P.D. Brimicombe, R.R. Nair, T.J. Booth, D. Jiang, F. Schedin, L.A. Ponomarenko, S.V. Morozov, H.F. Gleeson, E.W. Hill, A.K. Geim, and K.S. Novoselov, Nano Lett. 8, 1704 (2008).
A.J. Du, Z.H. Zhu, and S.C. Smith, J. Am. Chem. Soc. 132, 2876 (2010).
I.V. Pavlidis, T. Vorhaben, D. Gournis, G.K. Papadopoulos, U.T. Bornscheuer, and H. Stamatis, J. Nanoparticle Res. 14, 842 (2012).
L. Zhang, J. Xia, Q. Zhao, L. Liu, and Z. Zhang, Small 6, 537 (2010).
Q. Zhang, E. Uchaker, S.L. Candelaria, and C. Guozhong, Chem. Soc. Rev. 42, 3127 (2013).
B.E. Conway, Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications (New York: Kluwer Academic/Plenum, 1999).
L. Nyholm, G. Nyström, A. Mihranya, and M. Strømme, Adv. Mater. 23, 3751 (2011).
J.T.W. Wang, J.M. Ball, E.M. Barea, A. Abate, J.A.A. Webber, J. Huang, M. Saliba, I.M. Sero, J. Bisquert, H.J. Snaith, and R.J. Nicholas, Nano Lett. 14, 724 (2014).
M. Liu, R. Zhang, and W. Chen, Chem. Rev. 114, 5117 (2014).
B. Luo, S.M. Liu, and L.J. Zhi, Small 8, 630 (2012).
D.A. Dikin, S. Stankovich, E.J. Zimney, R.D. Piner, G.H.B. Dommett, G. Evmenenko, S.T. Nguyen, and R.S. Ruoff, Nature 448, 457 (2007).
J.T. Robinson, M. Zalalutdinov, J.W. Baldwin, F.K. Perkins, E.S. Snow, Z. Wei, P.E. Sheeshan, and B.H. Houston, Nano Lett. 8, 3441 (2008).
J.T. Robinson, F.K. Perkins, E.S. Snow, Z. Wei, and P.E. Sheeshan, Nano Lett. 8, 3137 (2008).
X. Zuo, S. He, D. Li, C. Peng, Q. Huang, S. Song, and C. Fan, Langmuir 26, 1936 (2010).
C. Jafta, F. Nkosi, L. Roux, M. Mathe, M. Kebede, K. Makgopa, Y. Song, D. Tong, M. Oyama, N. Manyala, S. Chen, and K. Ozoemena, Electrochim. Acta 110, 228 (2013).
A.H.C. Neto, F. Guinea, N.M.R. Peres, K.S. Novoselov, and A.K. Geim, Rev. Mod. Phys. 81, 109 (2009).
J. Xia, Q. Kuang, S. Yang, F. Xia, S. Wang, and L. Guo, Sci. Rep. 3, 2300 (2013).
L. Wang, Y. Li, Z. Han, L. Chen, B. Qian, X. Jiang, J. Pinto, and G. Yang, J. Mater. Chem. A 1, 8385 (2013).
J.A. Roger and Y.G. Huang, Proc. Natl. Acad. Sci. USA 106, 10875 (2009).
D.H. Kim, N. Lu, R. Ma, Y.S. Kim, R.H. Kim, S. Wang, J. Wu, S.M. Won, H. Tao, and A. Islam, et al., Science 333, 838 (2011).
R. Kötz and M. Carlen, Electrochim. Acta 45, 2483 (2000).
L.-Q. Mai, F. Yang, Y.-L. Zhao, X. Xu, L. Xu, and Y.-Z. Luo, Nat. Commun. 2, 381 (2011).
V.V.N. Obreja, Physica E 40E, 2596 (2008).
E. Frackowiak and F. Béguin, Carbon 39, 937 (2001).
C. Peng, S. Zhang, D. Jewell, and G.Z. Chen, Prog. Nat. Sci. 18, 177 (2008).
W. Sugimoto, K. Yokoshima, Y. Murakami, and Y. Takasu, Electrochim. Acta 52, 1742 (2006).
P. Simon and Y. Gogotsi, Nat. Mater. 7, 845 (2008).
Z.S. Wu, W. Ren, D.W. Wang, F. Li, B. Liu, and H.M. Cheng, ACS Nano 4, 5835 (2010).
C. Zhu, S. Guo, Y. Fang, L. Han, E. Wang, and S. Dong, Nano Res. 4, 648 (2011).
X. Lang, A. Hirata, T. Fujita, and M. Chen, Nat. Nanotechnol. 6, 232 (2011).
Y. Sun, X. Hu, W. Luo, and Y. Huang, ACS Nano 5, 7100 (2011).
Y. Liang, Y. Li, H. Wang, and H. Dai, J. Am. Chem. Soc. 135, 2013 (2013).
J. Zhang, J. Jiang, and X.S. Zhao, J. Phys. Chem. C 115, 6448 (2011).
G. Aminoff, Z. Kristallgr. 64, 475 (1927).
J. Attenburrow, A.F.B. Cameron, J.H. Chapman, R.M. Evans, B.A. Hems, A.B.A. Jansen, and T. Walker, J. Chem. Soc. 1094 (1952).
J. Coraux, L. Marty, N. Bendiab, and V. Bouchiat, Acc. Chem. Res. 46, 2193 (2013).
S. Cui, S. Mao, G. Lu, and J. Chen, J. Phys. Chem. Lett. 4, 2441 (2013).
V. Sridharm, H.-J. Kim, J.-W. Jung, C. Lee, S. Park, and I.-K. Oh, ACS Nano 6, 10562 (2012).
Z. Xu, Z. Li, C.M.B. Holt, X. Tan, H. Wang, B.S. Amirkhiz, T. Stephenson, and D. Mitlin, J. Phys. Chem. Lett. 3, 2928 (2012).
T. Kyotani, K. Suzuki, H. Yamashita, and A. Tomita, Tanso 160, 255 (1993).
T. Nakajima, A. Mabuchi, and R. Hagiwara, Carbon 26, 357 (1988).
W. Scholz and H.P.Z. Boehm, Anorg. Allg. Chem. 369, 327 (1969).
M. Ding, Y. Tang, and A. Star, J. Phys. Chem. Lett. 4, 147 (2013).
W. Wei, X. Cui, W. Chen, and D.G. Ivey, Chem. Soc. Rev. 40, 1697 (2011).
W. Hummers and R.J. Offeman, Am. Chem. Soc. 80, 1339 (1958).
S. Park, J. An, R.J. Potts, A. Velamakanni, S. Murali, and R.S. Ruoff, Carbon 49, 3019 (2011).
K.E. Carr, Carbon 8, 245 (1970).
D.C. Marcano, D.V. Kosynkin, J.M. Berlin, A. Sintskii, Z. Sun, A. Slesarev, L.B. Alemany, W. Lu, and J.M. Tour, ACS Nano 4, 4806 (2010).
M. Ding, Y. Tang, and A. Star, J. Phys. Chem. Lett. 4, 147 (2013).
H. Lipson and A.R. Stokes, Nature 149, 328 (1942).
O. Zhou, R.M. Fleming, D.W. Murphy, C.H. Chen, R.C. Haddon, and A.P. Ramirez, Science 263, 1744 (1994).
F. Buciuman, F. Patcas, R. Cracium, and D.R.T. Zahn, Phys. Chem. Chem. Phys. 1, 185 (1999).
C. Julien, M. Massot, R. Baddour-Hadjean, S. Franger, S. Bach, and J.P. Pereira-Ramos, Solid State Ion. 159, 345 (2003).
C. Julien, M. Massot, S. Rangan, M. Lemal, and D. Guyomard, J. Raman Spectrosc. 33, 223 (2002).
C.M. Julien, M. Massot, and C. Poinsignon, Spectrochim. Acta. A 60, 689 (2004).
A.C. Ferrari, Solid State Commun. 143, 47 (2007).
Z.W. Chen, J.K.L. Lai, and C.H. Shek, Appl. Phys. Lett. 86, 181911 (2005).
B.R. Strohmeier and D.M. Hercules, J. Phys. Chem. 88, 4923 (1988).
F. Kapteijn, A.D. Van Langeveld, J.A. Moulijn, A. Andreini, M.A. Vuurman, A.M. Turek, J.-M. Jehng, and I.E. Wachs, J. Catal. 150, 94 (1994).
D. Gosztola and M.J. Weaver, J. Electroanal. Chem. Interfacial Electrochem. 271, 141 (1989).
M.-C. Bernard, A.H.L. Go, V.B. Thi, and S.C. de Torresi, J. Electrochem. Soc. 140, 3065 (1993).
W.B. White and V.G. Keramidas, Spectrochim. Acta A 28, 501 (1972).
I. Rusakova, T.O. Ely, C. Hofmann, D.P. Centurion, C.S. Levin, N.J. Halas, A. Luttge, and K.H. Whitmire, Chem. Mater. 19, 1369 (2007).
C.M. Julien and M. Massot, J. Phys. Condens. Matter 15, 3151 (2003).
D.P. Dubal, D.S. Dhawale, R.R. Salunkhe, and C.D. Lokhande, J. Alloys Compd. 496, 370 (2010).
L.G. Cancado, K. Takai, T. Enoki, M. Endo, Y.A. Kim, H. Mizusaki, A. Jorio, L.N. Coelho, R. Magalhaes-Paniago, and M.A. Pimenta, Appl. Phys. Lett. 88, 163106 (2006).
K. Sato, R. Saito, Y. Oyama, J. Jiang, L.G. Cancado, M.A. Pimenta, A. Jorio, G. Ge Samsonidze, G. Dresselhaus, and M.S. Dresselhaus, Chem. Phys. Lett. 427, 117 (2006).
J.S. Park, A. Reina, R. Saito, J. Kong, G. Dresselhaus, and M.S. Dresselhaus, Carbon 47, 1303 (2009).
M.W. Iqbal, A.K. Singh, M.Z. Iqbal, and J. Eom, J. Phys. Condens. Matter 24, 335301 (2012).
X.F. Tang, J.H. Li, and J.M. Hao, Mater. Res. Bull. 43, 2912 (2008).
Y. Sun, P. Lv, J.-Y. Yang, L. He, J.-C. Nie, X. Liu, and Y. Li, Chem. Commun. 47, 11279 (2011).
X.F. Tang, J.H. Li, and J.M. Hao, Mater. Res. Bull. 43, 2912 (2008).
X.W. Xie, Y. Li, and Z.Q. Liu, Nature 458, 746 (2009).
L.H. Hu, Q. Peng, and Y.D. Li, J. Am. Chem. Soc. 130, 16136 (2008).
L. Hu, K. Sun, Q. Peng, B. Xu, and Y. Li, Nano Res. 3, 363 (2010).
J. Jansson, J. Catal. 194, 55 (2000).
P. Broqvist, I. Panas, and H. Persson, J. Catal. 210, 198 (2002).
M.C. Toroker, D.A. Kanan, N. Alidoust, L.Y. Isseroff, P. Liao, and E.A. Carter, Phys. Chem. Chem. Phys. 13, 16644 (2011).
F. Grillo, M.M. Natile, and B. Glisenti, Appl. Catal. B 48, 267 (2004).
V.V. Ilyasov, D.A. Velikokhatskii, I.V. Ershov, I.Y. Nikiforov, and T.P. Zhdanova, J. Struct. Chem. 52, 849 (2011); ibid. J. Mod. Phys. 2, 1120 (2011).
Acknowledgements
S.G. acknowledges partial financial support from the WKU Research Foundation for start-up funds and an NSF EPSCoR Track RII Award. We thank P. Norris (Advanced Materials Institute, WKU) for AFM training, E. Heintzman for SEM, and Dr. J. Andersland for BEI/EDS measurements.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Gupta, S., van Meveren, M.M. & Jasinski, J. Graphene-Based Hybrids with Manganese Oxide Polymorphs as Tailored Interfaces for Electrochemical Energy Storage: Synthesis, Processing, and Properties. J. Electron. Mater. 44, 62–78 (2015). https://doi.org/10.1007/s11664-014-3429-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11664-014-3429-2