Abstract
Nanostructured MnO2 films were prepared via cathodic electrodeposition under potentiostatic condition. X-ray diffraction (XRD) analyses reveal that the deposited films possess the hexagonal phase of epsilon manganese dioxide (ε-MnO2). Fourier transform infrared (FTIR) spectroscopy studies also confirm the manganese dioxide phase of the deposited films. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) studies show that the film deposited at the potential of 0.2 V has a porous network structure which is made of sparsely distributed grains. Cyclic voltammetry studies show the maximum specific capacitance to be 259.4 F/g at the scan rate of 5 mV/s for the film deposited at the potential of 0.2 V, while the chrono charge-discharge measurements on the film exhibit the maximum specific capacitance to be 325.6 F/g at the current density of 1 mA/cm2. The variation in specific capacitance values of the films deposited at different potentials is attributed to different morphologies of the films.
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References
Conway BE (1999) Electrochemical supercapacitors scientific fundamentals and technological applications. Kluwer Academic/Plenum Press, New York
Martin W, Brodd RJ (2004) What are batteries, fuel cells, and supercapacitors. Chem Rev 104:4245–4269
Kotz R, Carlen M (2000) Principles and applications of electrochemical capacitors. Electrochim Acta 45:2483–2498
Patrice S, Gogotsi Y (2008) Materials for electrochemical capacitors. Nat Mater 7:845–854
Burke A (2000) Ultracapacitors: why, how, and where is the technology. J Power Sources 91:37–50
Conway BE, Birss V, Wojtowicz J (1997) The role and utilization of pseudocapacitance for energy storage by supercapacitors. J Power Sources 66:1–14
Sarangapani S, Tilak BV, Chen C-P (1996) Materials for electrochemical capacitors: theoretical and experimental constraints. J Electrochem Soc 143:3791–3799
Frackowiak E, Beguin F (2001) Carbon materials for the electrochemical storage of energy in capacitors. Carbon 39:937–950
Taberna PL, Simon P, Fauvarque JF (2003) Electrochemical characteristics and impedance spectroscopy studies of carbon-carbon supercapacitors. J Electrochem Soc 150:A292–A300
Ishikawa M, Morita M, Ihara M, Matsuda Y (1994) Electric double-layer capacitor composed of activated carbon fiber cloth electrodes and solid polymer electrolytes containing alkyl ammonium salts. J Electrochem Soc 141:1730–1734
Liu C, Yu Z, Neff D, Zhamu A, Jang BZ (2010) Graphene-based supercapacitor with an ultrahigh energy density. Nano Lett 10:4863–4868
Okajima K, Ikeda A, Kamoshita K, Sudoh M (2005) High rate performance of highly dispersed C60 on activated carbon capacitor. Electrochim Acta 51:972–977
Jureviciute I, Bruckenstein S (2003) Electrochemical activity of chemically deposited polypyrrole films. J Solid State Electrochem 7:554–560
Mi H, Zhang X, Yang S, Ye X, Luo J (2008) Polyaniline nanofibers as the electrode material for supercapacitors. Mater Chem Phys 112:127–131
Mastragostino M, Arbizzani C, Soavi F (2002) Conducting polymers as electrode materials in supercapacitors. Solid State Ionics 148:493–498
Naudin E, Ho HA, Branchaud S, Breau L, Bélanger D (2002) Electrochemical polymerization and characterization of poly(3-(4-fluorophenyl)thiophene) in pure ionic liquids. J Phys Chem B 106:10585–10593
Tripathi SK, Kumar A, Hashmi SA (2006) Electrochemical redox supercapacitors using PVdF-HFP based gel electrolytes and polypyrrole as conducting polymer electrode. Solid State Ionics 177:2979–2985
Zhao Y-Q, Zhang G-Q, Li H-L (2006) Electrochemical characterization on layered lithium ruthenate for electrochemical supercapacitors. Solid State Ionics 177:1335–1339
Jones DJ, Wortham E, Rozieˋre J, Favier F, Pascal J-L, Monconduit L (2004) Manganese oxide nanocomposites: preparation and some electrochemical properties. J Phys Chem Solids 65:235–239
Nathan T, Aziz A, Noor AF, Prabaharan SRS (2007) Nanostructured NiO for electrochemical capacitors: synthesis and electrochemical properties. J Solid State Electrochem 12:1003–1009
Wang GX, Chen Y, Konstantinov K, Yao J, J-ho A, Liu HK, Dou SX (2002) Nanosize cobalt oxides as anode materials for lithium-ion batteries. J Alloys Compd 340:L5–L10
Qu QT, Shi Y, Li LL, Guo WL, Wu YP, Zhang HP, Guan SY, Holze R (2009) V2O5·0.6H2O nanoribbons as cathode material for asymmetric supercapacitor in K2SO4 solution. Electrochem Commun 11:1325–1328
Li Y, Chang S, Liu X, Huang J, Yin J, Wang G, Cao D (2012) Nanostructured CuO directly grown on copper foam and their supercapacitance performance. Electrochim Acta 85:393–398
Zheng JP, Cygan PJ, Jow TR (1995) Hydrous ruthenium oxide as an electrode material for electrochemical capacitors. J Electrochem Soc 142:2699–2703
Broughton JN, Brett MJ (2005) Variations in MnO2 electrodeposition for electrochemical capacitors. Electrochim Acta 50:4814–4819
Huang M, Li F, Dong F, Zhang YX, Zhang LL (2015) MnO2-based nanostructures for high-performance supercapacitors. J Mater Chem A 3:21380–21423
Chang J-K, Chen Y-L, Tsai W-T (2004) Effect of heat treatment on material characteristics and pseudo-capacitive properties of manganese oxide prepared by anodic deposition. J Power Sources 135:344–353
Prasad KR, Miura N (2004) Potentiodynamically deposited nanostructured manganese dioxide as electrode material for electrochemical redox supercapacitors. J Power Sources 135:354–360
Pang S-C, Anderson MA, Chapman TW (2000) Novel electrode materials for thin-film ultracapacitors: comparison of electrochemical properties of sol-gel-derived and electrodeposited manganese dioxide. J Electrochem Soc 147:444–450
Shinomiya T, Gupta V, Miura N (2006) Effects of electrochemical-deposition method and microstructure on the capacitive characteristics of nano-sized manganese oxide. Electrochim Acta 51:4412–4419
Srinivasan V, Weidner JW (1997) An electrochemical route for making porous nickel oxide electrochemical capacitors. J Electrochem Soc 144:L210–L213
Yousefi T, Davarkhah R, Golikand AN, Mashhadizadeh MH (2013) Synthesis, characterization, and supercapacitor studies of manganese (IV) oxide nanowires. Mater Sci Semicond Process 16:868–876
Weia J, Cheonga M, Nagarajana N, Zhitomirskya I (2007) Cathodic electrodeposition of manganese oxides for electrochemical supercapacitors. ECS Trans 3:1–9
Li J, Zhitomirsky I (2009) Cathodic electrophoretic deposition of manganese dioxide films. Colloids and Surfaces A: Physicochem Eng Aspects 348:248–253
Hassan S, Suzuki M, El-Moneim AA (2012) Capacitive behavior of manganese dioxide/stainless steel electrodes at different deposition currents. American Journal of Materials Science 2:11–14
Ali GAM, Yusoff MM, Ng YH, Lim HN, Chong KF (2015) Potentiostatic and galvanostatic electrodeposition of manganese oxide for supercapacitor application: a comparison study. Curr Appl Phys 15:1143–1147
Yuqiu H, Hongcheng Z (2011) Cathodic potentiostatic electrodeposition and capacitance characterization of manganese dioxide film. International Conference on Nanotechnology and Biosensors IPCBEE, vol 2. IACSIT Press, Singapore
Reddy RN, Reddy RG (2004) Synthesis and electrochemical characterization of amorphous MnO2 electrochemical capacitor electrode material. J Power Sources 132:315–320
Zhang L, Gong H (2015) Improvement in flexibility and volumetric performance for supercapacitor application and the effect of Ni–Fe ratio on electrode behaviour. J Mater Chem A 3:7607–7615
Pourbaix M (1996) Atlas of electrochemical equilibria in aqueous solutions. National Association of Corrosion Engineers, Houston
Jacob GM, Zhitomirsky I (2008) Microstructure and properties of manganese dioxide films prepared by electrodeposition. Appl Surf Sci 254:6671–6676
Xiao W, Xia H, Fuh J-Y-H LL (2009) Electrochemical synthesis and supercapacitive properties of ε-MnO2 with porous/nanoflaky hierarchical architectures. J Electrochem Soc 156:A627–A633
Zou R, Yuen MF, Zhang Z, Hu J, Zhang W (2015) Three-dimensional networked NiCo2O4/MnO2 branched nanowire heterostructure arrays on nickel foam with enhanced supercapacitor performance. J Mater Chem A 3:1717–1723
Bricker O (1965) Some stability relations in the system Mn–O2–H2O at 25° and one atmosphere total pressure. Am Mineral 50:1296–1354
Lee HY, Goodenough JB (1999) Supercapacitor behavior with KCl electrolyte. J Solid State Chem 144:220–223
Ragupathy P, Vasan HN, Munichandraiah N (2008) Synthesis and characterization of nano- MnO2 for electrochemical supercapacitor studies. J Electrochem Soc 155:A34–A40
Kuo S-L, Wu N-L (2006) Investigation of pseudocapacitive charge-storage reaction of MnO2 ∙ nH2O supercapacitors in aqueous electrolytes. J Electrochem Soc 153:A1317–A1324
Tran VM, Ha AT, Le MLP (2014) Capacitance behavior of nanostructured ε-MnO2/C composite electrode using different carbons matrix. Adv Nat Sci Nanosci Nanotechnol 5:025005 (9pp)
Minakshi M, Singh P, Issa TB, Thurgate S, Marco RD (2004) Lithium insertion into manganese dioxide electrode in MnO2/Zn aqueous battery part II. Comparison of the behavior of EMD and battery grade MnO2 in Zn|MnO2|aqueous LiOH electrolyte. J Power Sources 138:319–322
Pagnanelli F, Sambenedetto C, Furlani G, Veglio F, Toro L (2007) Preparation and characterisation of chemical manganese dioxide: effect of the operating conditions. J Power Sources 16:567–577
Adelkhani H, Ghaemi M, Jafari SM (2008) Novel nanostructured MnO2 prepared by pulse electrodeposition: characterization and electrokinetics. J Mater Sci Technol 24:857–862
Julien CM, Massot M, Poinsignon C (2004) Lattice vibrations of manganese oxides: part I. Periodic structures. Spectrochim Acta A 60:689–700
Jiang Y, Cui X, Zu L, Hu Z, Gan J, Lian H, Liu Y, Xing G (2015) High rate performance nanocomposite electrode of mesoporous manganese dioxide/silver nanowires in KI electrolytes. Nano 5:1638–1653
Dubal DP, Kim WB, Lokhande CD (2011) Surfactant assisted electrodeposition of MnO2 thin films: improved supercapacitive properties. J Alloys Compd 509:10050–10054
Zhang Y, Li G-Y, Lv Y, Wang L-Z, Zhang A-Q, Song Y-H, Huang B-L (2011) Electrochemical investigation of MnO2 electrode material for supercapacitors. Int J Hydrog Energy 36:11760–11766
Dubal DP, Kim WB, Lokhande CD (2012) Galvanostatically deposited Fe: MnO2 electrodes for supercapacitor application. J Phys Chem Solids 73:18–24
Jana SK, Rao VP, Banerjee S (2014) Enhancement of supercapacitance property of electrochemically deposited MnO2 thin films grown in acidic medium. Chem Phys Lett 593:160–164
Devaraj S, Munichandraiah N (2007) The effect of nonionic surfactant triton X-100 during electrochemical deposition of MnO2 on its capacitance properties. J Electrochem Soc 154:A901–A909
Bastidas JM, Polo JL, Cano E, Torres CL, Mora N (2000) Localised corrosion of highly alloyed stainless steels in an ammonium chloride and diethylamine chloride aqueous solution. Mater Corros 51:712–718
Silverman DC (1989) Corrosion rate estimation from pseudo-inductive electrochemical impedance response. Corrosion 45:824–830
Acknowledgements
The authors are grateful to Professor M. Aslam, IIT Bombay, for providing SEM, AFM, XRD, and Raman characterization facilities. Dr. Ajay K. Kushwaha is also thankful to DST, Government of India, for awarding prestigious “INSPIRE Faculty Award” (DST/INSPIRE/04/2015/002498).
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Sahay, P., Kushwaha, A.K. Electrochemical supercapacitive performance of potentiostatically cathodic electrodeposited nanostructured MnO2 films. J Solid State Electrochem 21, 2393–2405 (2017). https://doi.org/10.1007/s10008-017-3574-7
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DOI: https://doi.org/10.1007/s10008-017-3574-7