Abstract
The supercapacitor energy storage system has achieved a great attention, in future perspective, as compared to ordinary dielectric capacitors and batteries. The nature and type of electrode material employed in supercapacitor applications is critical to the electrochemical performance of a supercapacitor. Herein, co-precipitation derived Mn3O4 nanoparticles were mixed with graphite in a simple way and obtained uniformly mixed composite of exfoliated graphene with these nanoparticles. The electrochemical study of these composites revealed promising results for supercapacitor applications. X-ray diffraction study revealed the formation of single-phase Mn3O4 nanoparticles. The composite was probed for microstructural examination, by scanning electron microscopy, which revealed that Mn3O4 was uniformly embedded in exfoliated graphene sheets, aimed specifically for better electrochemical performance. The elemental composition was studied by energy dispersive X-rays spectroscopy and electrochemical performance of the composite deposited on Nickel foam for electrode using polyvinyl alcohol (PVA, 10%) as a binder has been examined by cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy in 1M K2SO4 electrolyte. In addition, different ratios of Mn3O4/graphene were prepared to investigate composition dependent performance of these composites. The highest value of specific capacitance achieved for composition (1:2) was 334 F/g at scan rate of 5 mVs−1.
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The authors declare that the data supporting the findings of this study are available within the paper. Should any raw data files be needed in another format they are available from the corresponding author upon reasonable request.
References
C. Liu, F. Li, L.P. Ma, H.M. Cheng, Advanced materials for energy storage. Adv. Mater. 22(8), E28–E62 (2010). https://doi.org/10.1002/adma.200903328
H. Wu, J. Mou, L. Zhou, Q. Zheng, N. Jiang, D. Lin, Cloud cap-like, hierarchically porous carbon derived from mushroom as an excellent host cathode for high performance lithium-sulfur batteries. Electrochim. Acta. 212, 1021–1030 (2016). https://doi.org/10.1016/j.electacta.2016.07.153
M. Saleem, G. Mehboob, M.S. Ahmed, S.N. Khisro, M.Z. Ansar, K. Mehmood, J.M. Ashfaq, Electrochemical properties of tin sulfide nano-sheets as cathode material for lithium-sulfur batteries. Front. Chem. 8, 254 (2020). https://doi.org/10.3389/fchem.2020.00254
P. Simon, Y. Gogotsi, Materials for electrochemical capacitors. Nat. Mater. 7(11), 845–854 (2008). https://doi.org/10.1038/nmat2297
Q. Rong, L.L. Long, X. Zhang, Y.X. Huang, H.Q. Yu, Layered cobalt nickel silicate hollow spheres as a highly-stable supercapacitor material. Appl. Energy. 153, 63–69 (2015). https://doi.org/10.1016/j.apenergy.2014.11.077
Y. Zhu, S. Murali, M.D. Stoller, K.J. Ganesh, W. Cai, P.J. Ferreira, R.S. Ruoff, Carbon-based supercapacitors produced by activation of graphene. Science. 332(6037), 1537–1541 (2011). https://doi.org/10.1126/Science.1200770
R. Ramachandran, M. Saranya, V. Velmurugan, B.P. Raghupathy, S.K. Jeong, A.N. Grace, Effect of reducing agent on graphene synthesis and its influence on charge storage towards supercapacitor applications. Appl. Energy. 153, 22–31 (2015). https://doi.org/10.1016/j.apenergy.2015.02.091
X. Su, L. Yu, G. Cheng, H. Zhang, M. Sun, L. Zhang, J. Zhang, Controllable hydrothermal synthesis of Cu-doped δ-MnO2 films with different morphologies for energy storage and conversion using supercapacitors. Appl. Energy 134, 439–445 (2014). https://doi.org/10.1016/j.apenergy.2014.08.050
J.P. Zheng, P.J. Cygan, T.R. Jow, Hydrous ruthenium oxide as an electrode material for electrochemical capacitors. J. Electrochem. Soc. 142(8), 2699 (1995). https://doi.org/10.1149/1.2050077
O.S. Yakovenko, L.Y. Matzui, L.L. Vovchenko, O.V. Lozitsky, O.I. Prokopov, O.A. Lazarenko, A.V. Trukhanov, Electrophysical properties of epoxy-based composites with graphite nanoplatelets and magnetically aligned magnetite. Mol. Cryst. Liq. Cryst. 661(1), 68–80 (2018). https://doi.org/10.1080/15421406.2018.1460243
W. Li, K. Xu, L. An, F. Jiang, X. Zhou, J. Yang, J. Hu, Effect of temperature on the performance of ultrafine MnO2 nanobelt supercapacitors. J. Mater. Chem. A 2(5), 1443–1447 (2014). https://doi.org/10.1039/C3TA14182A
Y. Munaiah, B.G.S. Raj, T.P. Kumar, P. Ragupathy, Facile synthesis of hollow sphere amorphous MnO2: the formation mechanism, morphology and effect of a bivalent cation-containing electrolyte on its supercapacitive behavior. J. Mater. Chem. A 1(13), 4300–4306 (2013). https://doi.org/10.1039/C3TA01089A
S. Devaraj, G.S. Gabriel, S.R. Gajjela, P. Balaya, Mesoporous MnO2 and its capacitive behavior. Electrochem. Solid-State Lett. 15(4), A57 (2012). https://doi.org/10.1149/2.016204esl
S. Chen, F. Liu, Q. Xiang, X. Feng, G. Qiu, Synthesis of Mn2O3 microstructures and their energy storage ability studies. Electrochim. Acta 106, 360–371 (2013). https://doi.org/10.1016/j.electacta.2013.06.001
B.G.S. Raj, A.M. Asiri, J.J. Wu, S. Anandan, Synthesis of Mn3O4 nanoparticles via chemical precipitation approach for supercapacitor application. J. Alloys Compd. 636, 234–240 (2015). https://doi.org/10.1016/j.jallcom.2015.02.164
R.K. Selvan, I. Perelshtein, N. Perkas, A. Gedanken, Synthesis of hexagonal-shaped SnO2 nanocrystals and SnO2@C nanocomposites for electrochemical redox supercapacitors. J. Phys. Chem. C 112(6), 1825–1830 (2008). https://doi.org/10.1021/jp076995q
X. Liu, Q. Long, C. Jiang, B. Zhan, C. Li, S. Liu, X. Dong, Facile and green synthesis of mesoporous Co3O4 nanocubes and their applications for supercapacitors. Nanoscale 5(14), 6525–6529 (2013). https://doi.org/10.1039/C3NR00495C
A. Devadas, S. Baranton, T.W. Napporn, C. Coutanceau, Tailoring of RuO2 nanoparticles by microwave assisted instant method for energy storage applications. J. Power Sources 196(8), 4044–4053 (2011). https://doi.org/10.1016/j.jpowsour.2010.11.149
D. Han, P. Xu, X. Jing, J. Wang, P. Yang, Q. Shen, M. Zhang, Trisodium citrate assisted synthesis of hierarchical NiO nanospheres with improved supercapacitor performance. J. Power Sources. 235, 45–53 (2013). https://doi.org/10.1016/j.jpowsour.2013.01.180
H. Lv, Y. Yuan, Q. Xu, H. Liu, Y.G. Wang, Y. Xia, Carbon quantum dots anchoring MnO2/graphene aerogel exhibits excellent performance as electrode materials for supercapacitor. J. Power Sources 398, 167–174 (2018). https://doi.org/10.1016/j.jpowsour.2018.07.059
T. Yousefi, A.N. Golikand, M.H. Mashhadizadeh, M. Aghazadeh, High temperature and low current density synthesis of Mn3O4 porous nano spheres: characterization and electrochemical properties. Curr. Appl. Phys. 12(2), 544–549 (2012). https://doi.org/10.1016/j.cap.2011.08.018
V. Subramanian, H. Zhu, B. Wei, Synthesis and electrochemical characterizations of amorphous manganese oxide and single walled carbon nanotube composites as supercapacitor electrode materials. Electrochem. Commun. 8(5), 827–832 (2006). https://doi.org/10.1016/j.elecom.2006.02.027
L. Li, K.H. Seng, H. Liu, I.P. Nevirkovets, Z. Guo, Synthesis of Mn3O4-anchored graphene sheet nanocomposites via a facile, fast microwave hydrothermal method and their supercapacitive behavior. Electrochim. Acta 87, 801–808 (2013). https://doi.org/10.1016/j.electacta.2012.08.127
K. Makgopa, K. Raju, P.M. Ejikeme, K.I. Ozoemena, High-performance Mn3O4/onion-like carbon (OLC) nanohybrid pseudocapacitor: unravelling the intrinsic properties of OLC against other carbon supports. Carbon 117, 20–32 (2017). https://doi.org/10.1016/j.carbon.2017.02.050
S. Li, L.L. Yu, Y.T. Shi, J. Fan, R.B. Li, G.D. Fan, J.T. Zhao, Greatly enhanced faradic capacities of 3D porous Mn3O4/G composites as lithium-ion anodes and supercapacitors by C–O–Mn bonding. ACS Appl. Mater. Interfaces. 11(10), 10178–10188 (2019). https://doi.org/10.1021/acsami.8b21063
A.V. Trukhanov, V.O. Turchenko, I.A. Bobrikov, S.V. Trukhanov, I.S. Kazakevich, A.M. Balagurov, Crystal structure and magnetic properties of the BaFe12–xAlxO19 (x = 0.1–1.2) solid solutions. J. Magn. Magn. Mater. 393, 253–259 (2015). https://doi.org/10.1016/j.jmmm.2015.05.076
M.V. Zdorovets, A.L. Kozlovskiy, D.I. Shlimas, D.B. Borgekov, Phase transformations in FeCo–Fe2CoO4/Co3O4-spinel nanostructures as a result of thermal annealing and their practical application. J. Mater. Sci.: Mater. Electron. 32(12), 16694–16705 (2021). https://doi.org/10.1007/s10854-021-06226-5
E. Iyyamperumal, S. Wang, L. Dai, Vertically aligned BCN nanotubes with high capacitance. ACS nano. 6(6), 5259–5265 (2012). https://doi.org/10.1021/nn301044v
J. Zhu, J. Jiang, Y. Feng, G. Meng, H. Ding, X. Huang, Three-dimensional Ni/SnOx/C hybrid nanostructured arrays for lithium-Ion microbattery anodes with enhanced areal capacity. ACS Appl. Mater. Interfaces 5(7), 2634–2640 (2013). https://doi.org/10.1021/am400055a
J. Luo, X. Xia, Y. Luo, C. Guan, J. Liu, X. Qi, H.J. Fan, Rationally designed hierarchical TiO2@Fe2O3 hollow nanostructures for improved lithium ion storage. Adv. Energy Mater. 3(6), 737–743 (2013). https://doi.org/10.1002/aenm.201200953
Y. Luo, J. Luo, W. Zhou, X. Qi, H. Zhang, Y.W. Denis, T. Yu, Controlled synthesis of hierarchical graphene-wrapped TiO2@Co3O4 coaxial nanobelt arrays for high-performance lithium storage. J. Mater. Chem. A 1(2), 273–281 (2013). https://doi.org/10.1039/C2TA00064D
Q. Wang, X. Wang, B. Liu, G. Yu, X. Hou, D. Chen, G. Shen, NiCo2O4 nanowire arrays supported on Ni foam for high-performance flexible all-solid-state supercapacitors. J. Mater. Chem. A 1(7), 2468–2473 (2013). https://doi.org/10.1039/C2TA01283A
H. Hu, B. Guan, B. Xia, X.W. Lou, Designed formation of Co3O4/NiCo2O4 double-shelled nanocages with enhanced pseudocapacitive and electrocatalytic properties. J. Am. Chem. Soc. 137(16), 5590–5595 (2015). https://doi.org/10.1021/jacs.5b02465
M. Huang, X.L. Zhao, F. Li, W. Li, B. Zhang, Y.X. Zhang, Synthesis of Co3O4/SnO2@MnO2 core–shell nanostructures for high-performance supercapacitors. J. Mater. Chem. A 3(24), 12852–12857 (2015). https://doi.org/10.1039/C5TA02144H
Q.J. Le, M. Huang, T. Wang, X.Y. Liu, L. Sun, X.L. Guo, Y.X. Zhang, Biotemplate derived three dimensional nitrogen doped graphene@MnO2 as bifunctional material for supercapacitor and oxygen reduction reaction catalyst. J. Colloid Interface Sci. 544, 155–163 (2019). https://doi.org/10.1016/j.jcis.2019.02.089
S. Khamlich, T. Mokrani, M.S. Dhlamini, B.M. Mothudi, M. Maaza, Microwave-assisted synthesis of simonkolleite nanoplatelets on nickel foam–graphene with enhanced surface area for high-performance supercapacitors. J. Colloid Interface Sci. 461, 154–161 (2016). https://doi.org/10.1016/j.jcis.2015.09.033
S. Khamlich, A. Bello, M. Fabiane, B.D. Ngom, N. Manyala, Hydrothermal synthesis of simonkolleite microplatelets on nickel foam-graphene for electrochemical supercapacitors. J. Solid State Electrochem. 17, 2879–2886 (2013). https://doi.org/10.1007/s10008-013-2206-0
M. Fabiane, S. Khamlich, A. Bello, J. Dangbegnon, D. Momodu, A.T. Charlie Johnson, N. Manyala, Growth of graphene underlayers by chemical vapor deposition. AIP Adv. (2013). https://doi.org/10.1063/1.4834975
Z. Chen, W. Ren, L. Gao, B. Liu, S. Pei, H.M. Cheng, Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition. Nat. Mater. 10(6), 424–428 (2011). https://doi.org/10.1038/nmat3001
S. Li, L.L. Yu, R.B. Li, J. Fan, J.T. Zhao, Template-free and room-temperature synthesis of 3D sponge-like mesoporous Mn3O4 with high capacitive performance. Energy Storage Mater. 11, 176–183 (2018). https://doi.org/10.1016/j.ensm.2017.07.011
D.A. Vinnik, V.E. Zhivulin, D.P. Sherstyuk, A.Y. Starikov, P.A. Zezyulina, S.A. Gudkova, A.V. Trukhanov, Ni substitution effect on the structure, magnetization, resistivity and permeability of zinc ferrites. J. Mater. Chem. C 9(16), 5425–5436 (2021). https://doi.org/10.1039/D0TC05692H
D.A. Vinnik, V.E. Zhivulin, D.P. Sherstyuk, A.Y. Starikov, P.A. Zezyulina, S.A. Gudkova, A.V. Trukhanov, Electromagnetic properties of zinc–nickel ferrites in the frequency range of 0.05–10 GHz. Mater. Today Chem. 20, 100460 (2021). https://doi.org/10.1016/j.mtchem.2021.100460
H.N. Miankushki, A. Sedghi, S. Baghshahi, A comparison of the electrochemical properties of graphene/Mn3O4 composites fabricated by two different methods. Int. J. Electrochem. Sci. 13, 2462–2473 (2018)
S. Maharubin, X. Zhang, F. Zhu, H.C. Zhang, G. Zhang, Y. Zhang, Synthesis and applications of semiconducting graphene. J. Nanomater. (2016). https://doi.org/10.1155/2016/6375962
J.W. Lee, A.S. Hall, J.D. Kim, T.E. Mallouk, A facile and template-free hydrothermal synthesis of Mn3O4 nanorods on graphene sheets for supercapacitor electrodes with long cycle stability. Chem. Mater. 24(6), 1158–1164 (2012). https://doi.org/10.1021/cm203697w
G.S. Gund, D.P. Dubal, B.H. Patil, S.S. Shinde, C.D. Lokhande, Enhanced activity of chemically synthesized hybrid graphene oxide/Mn3O4 composite for high performance supercapacitors. Electrochim. Acta 92, 205–215 (2013). https://doi.org/10.1016/j.electacta.2012.12.120
L. Wang, Y. Li, Z. Han, L. Chen, B. Qian, X. Jiang, G. Yang, Composite structure and properties of Mn3O4/graphene oxide and Mn3O4/graphene. J. Mater. Chem. A 1(29), 8385–8397 (2013). https://doi.org/10.1039/C3TA10237H
C. Chen, H. Jian, K. Mai, Z. Ren, J. Wang, X. Fu, Z. Wang, Shape-and size-controlled synthesis of Mn3O4 nanocrystals at room temperature. Eur. J. Inorg. Chem. 2014(19), 3023–3029 (2014). https://doi.org/10.1002/ejic.201400013
K.K. Kadyrzhanov, D.I. Shlimas, A.L. Kozlovskiy, M.V. Zdorovets, Research of the shielding effect and radiation resistance of composite CuBi2O4 films as well as their practical applications. J. Mater. Sci.: Mater. Electron. 31, 11729–11740 (2020). https://doi.org/10.1007/s10854-020-03724-w
R.I. Shakirzyanov, A.L. Kozlovskiy, M.V. Zdorovets, A.L. Zheludkevich, D.I. Shlimas, N.V. Abmiotka, A.V. Trukhanov, Impact of thermobaric conditions on phase content, magnetic and electrical properties of the CoFe2O4 ceramics. J. Alloys Compd. 954, 170083 (2023). https://doi.org/10.1016/j.jallcom.2023.170083
G. Mustafa, G. Mehboob, S.N. Khisro, M. Javed, X. Chen, M.S. Ahmed, G. Mehboob, Facile synthesis and electrochemical studies of Mn2O3/graphene composite as an electrode material for supercapacitor application. Frontiers in chemistry 9, 717074 (2021). https://doi.org/10.3389/fchem.2021.717074
D. Feng, X. Pan, Q. Xia, J. Qin, Y. Zhang, X. Chen, Metallic MoS2 nanosphere electrode for aqueous symmetric supercapacitors with high energy and power densities. J. Mater. Sci. 55(2), 713–723 (2020). https://doi.org/10.1007/s10853-019-03997-5
A. Vázquez-Olmos, R. Redón, G. Rodríguez-Gattorno, M.E. Mata-Zamora, F. Morales-Leal, A.L. Fernández-Osorio, J.M. Saniger, One-step synthesis of Mn3O4 nanoparticles: structural and magnetic study. J. Colloid Interface Sci. 291(1), 175–180 (2005). https://doi.org/10.1016/j.jcis.2005.05.005
S.V. Trukhanov, M.V. Bushinsky, I.O. Troyanchuk, H. Szymczak, Magnetic ordering in La1–xSrxMnO3–x/2 anion-deficient manganites. J. Exp. Theor. Phys. 99, 756–765 (2004). https://doi.org/10.1134/1.1826167
A. Kozlovskiy, K. Egizbek, M.V. Zdorovets, M. Ibragimova, A. Shumskaya, A.A. Rogachev, K. Kadyrzhanov, Evaluation of the efficiency of detection and capture of manganese in aqueous solutions of FeCeOx nanocomposites doped with Nb2O5. Sensors 20(17), 4851 (2020). https://doi.org/10.3390/s20174851
Y. Kong, R. Jiao, S. Zeng, C. Cui, H. Li, S. Xu, L. Wang, Study on the synthesis of Mn3O4 nanooctahedrons and their performance for lithium ion batteries. Nanomaterials 10(2), 367 (2020). https://doi.org/10.3390/nano10020367
T. Wang, Q. Le, X. Guo, M. Huang, X. Liu, F. Dong, Y.X. Zhang, Preparation of porous graphene@Mn3O4 and its application in the oxygen reduction reaction and supercapacitor. ACS Sustain. Chem. Eng. 7(1), 831–837 (2018). https://doi.org/10.1021/acssuschemeng.8b04447
O.S. Yakovenko, L.Y. Matzui, L.L. Vovchenko, A.V. Trukhanov, I.S. Kazakevich, S.V. Trukhanov, U. Ritter, Magnetic anisotropy of the graphite nanoplatelet–epoxy and MWCNT–epoxy composites with aligned barium ferrite filler. J. Mater. Sci. 52, 5345–5358 (2017). https://doi.org/10.1007/s10853-017-0776-4
M.C. Nwankwo, B. Ezealigo, A.C. Nwanya, A.C. Nkele, A. Agbogu, U. Chime, F.I. Ezema, Syntheses and characterizations of GO/Mn3O4 nanocomposite film electrode materials for supercapacitor applications. Inorg. Chem. Commun. 119, 107983 (2020)
H. Wang, L. Pilon, Physical interpretation of cyclic voltammetry for measuring electric double layer capacitances. Electrochim. Acta. 64, 130–139 (2012). https://doi.org/10.1016/j.electacta.2011.12.118
S. Li, A. Thomas, Emerged carbon nanomaterials from metal-organic precursors for electrochemical catalysis in energy conversion, in Advanced nanomaterials for electrochemical-based energy conversion and storage. (Elsevier, Amsterdam, 2020), pp.393–423. https://doi.org/10.1016/B978-0-12-814558-6.00012-5
P.S. Nnamchi, C.S. Obayi, Electrochemical characterization of nanomaterials, in Characterization of nanomaterials. (Woodhead Publishing, Sawston, 2018), pp.103–127. https://doi.org/10.1016/B978-0-08-101973-3.00004-3
J. Zhang, J. Wu, H. Zhang, PEM fuel cell Testing and Diagnosis (Newnes.Books.google.com, 2013)
J. Liu, J. Wang, C. Xu, H. Jiang, C. Li, L. Zhang, Z.X. Shen, Advanced energy storage devices: basic principles, analytical methods, and rational materials design. Adv. Sci. 5(1), 1700322 (2018). https://doi.org/10.1002/advs.201700322
M.I.T.I.V. Student, Transport Phenomena Lecture 37: Pseudocapacitors and batteries. http://ocw.mit.edu/terms
W. Zeng, Y. Huang, Y. Xiong, N. Wang, C. Xu, L. Huang, Gas bubble templated synthesis of Mn3O4-embedded hollow carbon nanospheres in ethanol flame for elastic supercapacitor. J. Alloys Compd. 731, 210–221 (2018). https://doi.org/10.1016/j.jallcom.2017.10.006
Y. Hu, Y. Wu, J. Wang, Manganese-oxide‐based electrode materials for energy storage applications: how close are we to the theoretical capacitance? Adv. Mater. 30(47), 1802569 (2018). https://doi.org/10.1002/adma.201802569
G. Jin, X. Xiao, S. Li, K. Zhao, Y. Wu, D. Sun, F. Wang, Strongly coupled graphene/Mn3O4 composite with enhanced electrochemical performance for supercapacitor electrode. Electrochim. Acta 178, 689–698 (2015). https://doi.org/10.1016/j.electacta.2015.08.032
L. Zhu, S. Zhang, Y. Cui, H. Song, X. Chen, One step synthesis and capacitive performance of graphene nanosheets/Mn3O4 composite. Electrochim. Acta 89, 18–23 (2013). https://doi.org/10.1016/j.electacta.2012.10.157
Acknowledgements
We acknowledge the South China Normal University for Electrochemical Analysis and National Centre for Physics Islamabad for X-ray analysis of prepared sample. This work was supported by Department of Physics university of Kotli Azad Jammu and Kashmir. We also thank the funding from the National Natural Science Foundation of China (62071459), National Key Research and Development Program of China (2022YFF1202500, 2022YFF1202502), International Science and Technology Cooperation of Guangdong Province (2022A0505050058), Foundation of Shenzhen (KQTD20210811090217009, JCYJ20220818101205011).
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SNK design the experiment. Ghulam Mustafa conducted the experiments and wrote the manuscript. Yanlong Tai and Gohar Mehboob helps writing, proof reading of the manuscript. Remaining authors contributed in different characterisation etc.
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Mustafa, G., Qi, K., Khademi, S. et al. Electrochemical performance of Mn3O4/graphene composite deposited on nickel foam as promising electrode material for supercapacitor application. J Mater Sci: Mater Electron 35, 383 (2024). https://doi.org/10.1007/s10854-024-12081-x
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DOI: https://doi.org/10.1007/s10854-024-12081-x