Abstract
This paper reports a novel strategy for preparing redox-active electrolyte through introducing a redox-mediator (p-phenylenediamine, PPD) into KOH electrolyte for the application of ball-milled MnO2-based supercapacitors. The morphology and compositions of ball-milled MnO2 were characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrochemical properties of the supercapacitor were evaluated by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) techniques. The introduction of p-phenylenediamine significantly improves the performance of the supercapacitor. The electrode specific capacitance of the supercapacitor is 325.24 F g−1, increased by 6.25 folds compared with that of the unmodified system (44.87 F g−1) at the same current density, and the energy density has nearly a 10-fold increase, reaching 10.12 Wh Kg−1. In addition, the supercapacitor exhibits good cycle-life stability.
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References
Conway BE. Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications, 2nd. New York: Kluwer Academic/ Plenum Publishers, 1999
Lang XY, Hirata A, Fujita T, Chen MW. Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors. Nat Nano, 2011, 6: 232–236
Hu CC, Chang KH, Lin MC, Wu YT. Design and tailoring of the nanotubular arrayed architecture of hydrous RuO2 for next generation supercapacitors. Nano Lett, 2006, 6: 2690–2695
Hu CC, Hung CY, Chang KH, Yang YL. A hierarchical nanostructure consisting of amorphous MnO2, Mn3O4 nanocrystallites, and single-crystalline MnOOH nanowires for supercapacitors. J Power Sources, 2011, 196: 847–850
Wei WF, Cui XW, Chen WX, Ivey DG. Manganese oxide-based materials as electrochemical supercapacitor electrodes. Chem Soc Rev, 2011, 40: 1697–1721
Ni JP, Lu WC, Zhang LM, Yue BH, Shang XF, Lv Y. Low-temperature synthesis of monodisperse 3D manganese oxide nanoflowers and their pseudocapacitance properties. J Phys Chem C, 2008, 113: 54–60
Zhao X, Johnston C, Crossley A, Grant PS. Printable magnetite and pyrrole treated magnetite based electrodes for supercapacitors. J Mater Chem, 2010, 20: 7637–7644
Meher SK, Justin P, Ranga RG. Microwave-mediated synthesis for improved morphology and pseudocapacitance performance of nickel oxide. Acs Appl Mater Inter, 2011, 3: 2063–2073
Feng Y, Zhang ML, Chen Y, Han Y, Shi ZH. Inorganic salt water solution reaction synthesis and capapcitor characteristics of nano-MnO2 powder. J Chin Cera Soc, 2005, 33: 318–322 (in chinese)
Wang HQ, Yang GF, Li QY, Zhong XX, Wang FP, Li ZS, Li YH. Porous nano-MnO2: Large scale synthesis via a facile quick-redox procedure and application in a supercapacitor. New J Chem, 2011, 35: 469–475
Su LH, Zhang XG, Mi CH, Gao B, Liu Y. Improvement of the capacitive performances for Co-Al layered double hydroxide by adding hexacyanoferrate into the electrolyte. Phys Chem Chem Phys, 2009, 11: 2195–2202
Sun GH, Li KX, Sun CG. Electrochemical performance of electrochemical capacitors using Cu(II)-containing ionic liquid as the electrolyte. Micropor Mesopor Mat, 2010, 128: 56–61
Roldán S, Blanco C, Granda M, Menéndez R, Santamaría R. Towards a further generation of high-energy carbon-based capacitors by using redox-active electrolytes. Angew Chemie Inte Ed, 2011, 50: 1699–1701
Yin YJ, Zhou JJ, Mansour AN, Zhou XY. Effect of NaI/I2 mediators on properties of PEO/LiAlO2 based all-solid-state supercapacitors. J Power Sources, 2011, 196: 5997–6002
Wu JH, Lan Z, Lin J, Huang ML, Hao SC, Sato T, Yin S. A novel thermosetting gel electrolyte for stable quasi-solid-state dye-sensitized solar cells. Adv Mater, 2007, 19: 4006–4011
Ke NJ, Lu SS, Cheng SH. A strategy for the determination of dopamine at a bare glassy carbon electrode: p-phenylenediamine as a nucleophile. Electrochem Commun, 2006, 8: 1514–1520
Li M, Yang CY, Zhou WK, Zhu M, Reversible oxidation of p-phenylenediamine on hemoglobin /poly(L-glutamic acid) /glassy carbon modified electrode. Chinese J App Chem, 2010, 9: 1093–1098 (in chinese)
Jiao K, Sun W, Zhang SS, Sun G. Application of p-phenylenediamine as an electrochemical substrate in peroxidase-mediated voltammetric enzyme immunoassay. Anal Chim Acta, 2000, 413: 71–78
Zhao WF, Fang M, Wu FR, Wu H, Wang LW, Chen GH. Preparation of graphene by exfoliation of graphite using wet ball milling. J Mater Chem, 2010, 20: 5817–5819
Zhang WX, Yang ZH, Wang X, Zhang YC, Wen XG, Yang SH. Large-scale synthesis of β-MnO2 nanorods and their rapid and efficient catalytic oxidation of methylene blue dye. Catal Commun, 2006, 7: 408–412
Hashmi SA, Kumar A, Tripathi SK. Investigations on electrochemical supercapacitors using polypyrrole redox electrodes and PMMA based gel electrolytes. Eur Polym J, 2005, 41: 1373–1379
Toupin M, Brousse T, Bélanger D. Charge storage mechanism of MnO2 electrode used in aqueous electrochemical capacitor. Chem Mater, 2004, 16: 3184–3190
Li F, Shi JJ, Qin X. Synthesis and supercapacitor characteristics of PANI/CNTs composites. Chinese Sci Bull, 2009, 54: 3900–3905 (in chinese)
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Yu, H., Wu, J., Fan, L. et al. Application of a novel redox-active electrolyte in MnO2-based supercapacitors. Sci. China Chem. 55, 1319–1324 (2012). https://doi.org/10.1007/s11426-012-4673-z
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DOI: https://doi.org/10.1007/s11426-012-4673-z