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Synthesis, characterization and electrical properties of polypyrrole/Mn0.8Zn0.2Fe2O4/GO ternary hybrid composites using spent Zn-C batteries

  • Original Paper: Nano-structured materials (particles, fibers, colloids, composites, etc.)
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Abstract

In this manuscript, ternary hybrid composites (PMG) have been synthesized via combination of polypyrrole (PPy), Mn-Zn ferrite (MZF) and graphite oxide (GO) components. The MZF was synthesized via acid leaching process of spent Zn-C batteries and green auto-combustion processes using different fuels. The in-situ polymerization process was then used to prepare the entire composites. XRD of ternary hybrids showed only broad peak characteristic of PPy without any indication for the MZF or GO suggesting the inclusion of MZF and GO into PPy matrix. In addition, the TEM images and EDS analysis exhibited that both MZF particles and GO layers are embedded and completely coated with PPy layers. FT-IR spectra of PMG composites indicated only identical bands to that of pure PPy. The very weak magnetic characters obtained using VSM further confirming the core-shell structure. TG curve of PMG ternary composite showed weight loss agrees well with the loss of all PPy and GO contents and confirms the weight ratio of MZF. It also showed that, the thermal stability of PPy was reduced by including in this entire composite attributed to the formed core-shell structure. An appropriate mechanism for the ternary hybrid composites formation was suggested and discussed. The electrical measurements exhibited constant behavior of conductivity by increasing temperature up to 420 K at which the dehydration and skeletal chain decomposition of both GO and PPy initiate. The GO does not greatly affected the conductivity due to the complete coating phenomena besides the pronouncing of PPy conductivity. Generally, the conductivities for all PMG composites are slightly dependent on the MZF preparation method and improved than that of pure PPy attributed to the presence of GO.

Graphical Abstract

Schematic diagram for the formation process of PPy/Mn0.8Zn0.2Fe2O4/GO (PMG) composites via in-situ polymerization process.

Research highlights

  • Mn0.8Zn0.2Fe2O4 was prepared using spent Zn-C batteries using variety of auto-combustion methods.

  • PPy/Mn0.8Zn0.2Fe2O4/GO (PMG) composites were prepared via in-situ polymerization.

  • An appropriate mechanism for the composites formation was suggested and discussed.

  • XRD indicated the complete coating of GO and MZF with the PPy matrix.

  • Effect of MZF preparation method on different properties could be neglected due to the coreshell structure formed.

  • Electrical measurements indicated that, GO does not greatly affected conductivity due tocomplete coating phenomena.

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References

  1. Riaz A, Qurat ul Ain, Kanwal F, Ishaq S, Khan AR, Mustafa GM, Abbas SK, Naseem S, Ramay SM, Atiq S (2020) Identification of frequency regimes for short and long range mobility of charge carriers in GO/MnFe2O4/PPy nanocomposites. Synth Met 263:116336

    Article  CAS  Google Scholar 

  2. Wu J, Ye Z, Liu W, Liu Z, Chen J (2017) The effect of GO loading on electromagnetic wave absorption properties of Fe3O4/reduced graphene oxide hybrids. Ceram Int 43:13146–13153

    Article  CAS  Google Scholar 

  3. Kuester S, Barra GM, Ferreira Jr JC, Soares BG, Demarquette NR (2016) Electromagnetic interference shielding and electrical properties of nanocomposites based on poly (styrene-b-ethylene-ran-butylene-b-styrene) and carbon nanotubes. Eur Poly J 77:43–53

    Article  CAS  Google Scholar 

  4. Zhu W, Wang L, Zhao R, Ren J, Lu G, Wang Y (2011) Electromagnetic and microwave-absorbing properties of magnetic nickel ferrite nanocrystals. Nanoscale 3:2862–2864

    Article  CAS  Google Scholar 

  5. Mariappan CR, Gajraj V, Gade S, Kumar A, Dsoke S, Indris S, Ehrenberg H, Prakash GV, Jose R (2019) Synthesis and electrochemical properties of rGO/polypyrrole/ferrites nanocomposites obtained via a hydrothermal route for hybrid aqueous supercapacitors. J Electroanal Chem 845:72–83

    Article  CAS  Google Scholar 

  6. Thu TV, Nguyen TV, Le XD, Le TS, Thuy VV, Huy TQ, Truong QD (2019) Graphene-MnFe2O4-polypyrrole ternary hybrids with synergistic effect for supercapacitor electrode. Electrochim Acta 314:151–160

    Article  CAS  Google Scholar 

  7. Qie L, Yuan LX, Zhang WX, Chen WM, Huang YH (2012) Revisit of polypyrrole as cathode material for lithium-ion battery. J Electrochem Soc 159:A1624–A1629

    Article  CAS  Google Scholar 

  8. Kandulna R, Choudhary R, Singh R (2019) Free exciton absorptions and quasi-reversible redox actions in polypyrrole–polyaniline–zinc oxide nanocomposites as electron transporting layer for organic light emitting diode and electrode material for supercapacitors. J Inorg Organomet Polym Mater 29:730–744

    Article  CAS  Google Scholar 

  9. Kang HC, Geckeler K (2000) Enhanced electrical conductivity of polypyrrole prepared by chemical oxidative polymerization: effect of the preparation technique and polymer additive. Polym 41:6931–6934

    Article  CAS  Google Scholar 

  10. Hussain HV, Ahmad M, Ansar MT, Mustafa GM, Ishaq S, Naseem S, Murtaza G, Kanwal F, Atiq S (2020) Polymer based nickel ferrite as dielectric composite for energy storage applications. Synth Met 268:116507

    Article  CAS  Google Scholar 

  11. Yang C, Zhang L, Hu N, Yang Z, Wei H, Zhang Y (2016) Reduced graphene oxide/Polypyrrole nanotube papers for flexible all-solid-state supercapacitors with excellent rate capability and high energy density. J Power Sources 302:39–45

    Article  CAS  Google Scholar 

  12. Ding L, Zhao X, Huang Y, Yan J, Li T, Liu P (2021) Ultra-broadband and covalently linked core–shell CoFe2O4@PPy nanoparticles with reduced graphene oxide for microwave absorption. J Colloid Interf Sci 595:168–177

    Article  CAS  Google Scholar 

  13. Gabal MA, Al-Harthy EA, Al Angari YM, Awad A, Al-Juaid AA, Abdel-Daiem AM, Abdu Saeed (2021) Recovery of Mn0.8Zn0.2Fe2O4 from Zn–C battery: auto-combustion synthesizes, characterization, and electromagnetic properties. J Sol-gel Sci Technol 100:1–12

    Article  Google Scholar 

  14. Gabal MA, Al-Harthy EA, Al Angari YM, Awad A, Al-Juaid AA, Hussein Mahmoud A, Abdel-Daiem AM, Sobahi TR, Abdu Saeed (2022) synthesis, structural, magnetic and high-frequency electrical properties of Mn0.8Zn0.2Fe2O4/polypyrrole core-shell composite using waste batteries, J Inorg Organomet Polym https://doi.org/10.1007/s10904-022-02241-z

  15. Xu Z, Fan J, Han Y, Liu T, Zhang H, Song K, Zhang C (2019) Preparation and characterization of Mn–Zn ferrites via nano-in-situ composite method. Sol Stat Sci 98:106006

    Article  CAS  Google Scholar 

  16. Shebla A, Hassan AA, Salama DM, Abd El-Aziz ME, Abd Elwahed MSA (2020) Template-free microwave-assisted hydrothermal synthesis of manganes-zinc ferrite as a nanofertilizer for squash plant (Cucurbita pepo L), Heliyon e03596

  17. Al-Hada NM, Kamari HM, Shaari Abdul H, Saion E (2019) Fabrication and characterization of Manganese–Zinc Ferrite nanoparticles produced utilizing heat treatment technique. Results Phys 12:1821–1825

    Article  Google Scholar 

  18. Lin Z, Xiaoling P, Xinqing W, Hongliang G, Jing Z, Yunwei X (2015) Preparation and characterization of manganese-zinc ferrites by a solvothermal method. Rare Met Mater Eng 44:1062–1066

    Article  Google Scholar 

  19. Limin D, Zhidong H, Yaoming Z, Ze W, Xianyou Z (2006) Preparation and sinterability of Mn-Zn ferrite powders by sol-gel method. J Rare Earths 24:54–56

    Article  Google Scholar 

  20. Mathew DS, Juang RS (2007) An overview of the structure and magnetism of spinel ferrite nanoparticles and their synthesis in microemulsions. Chem Eng J 129:51–65

    Article  CAS  Google Scholar 

  21. Angermann A, Topfer J (2011) Synthesis of nano-crystalline Mn–Zn ferrite powders through thermolysis of mixed oxalates. Ceram Int 37:995–1002

    Article  CAS  Google Scholar 

  22. Topfer J, Angermann A (2011) Nanocrystalline magnetite and Mn–Zn ferrite particles via the polyol process: Synthesis and magnetic properties. Mater Chem Phys 129:337–342

    Article  Google Scholar 

  23. Kim TH, Senanayake G, Kang JG, Sohn JS, Rhee KI, Lee SW, Shin SM (2009) Reductive acid leaching of spent zinc-carbon batteries and oxidative precipitation of Mn-Zn ferrite nanoparticles. Hydrometallurgy 96:154–158

    Article  CAS  Google Scholar 

  24. Gabal MA, Al-luhaibi RS, Al-Angari YM (2012) Mn-Zn nano-crystalline ferrites synthesized from spent Zn-C batteries using novel gelatin method. J Hazard Mater 246:227–233

    Google Scholar 

  25. Racz R, Ilea P (2013) Electrolytic recovery of Mn3O4 and Zn from sulphuric acid leach liquors of spent zincecarboneMnO2 battery powder. Hydrometallurgy 139:116–123

    Article  CAS  Google Scholar 

  26. Leao QC, Carlos AJ, Augusto VC, Gante V, Luiz MJ (2014) Recovery of manganese and zinc via sequential precipitation from spent zinc-MnO2 dry cells after fusion with potassium hydrogen sulfate. J Power Sources 248:596–603

    Article  Google Scholar 

  27. Qu J, Feng Y, Zhang Q, Cong Q, Luo C, Yuan X (2015) A new insight of recycling of spent Zn–Mn alkaline batteries: Synthesis of ZnxMn1-xO nanoparticles and solar light driven photocatalytic degradation of bisphenol A using them. J Alloy Compds 622:703–707

    Article  CAS  Google Scholar 

  28. Wang J, Tian B, Niu Z, Qi S, Bao Y, Xin B (2019) Synthesis of nano-sized Zn-Mn ferrite from the resulting bioleachate of obsolete Zn-Mn batteries at a high pulp density of 5.0% enhanced by the added Fe3+. J Clean Prod 229:299–307

    Article  CAS  Google Scholar 

  29. Wang Y, Shi Z, Huang Y, Ma Y, Wang C, Chen M, Chen Y (2009) Supercapacitor devices based on graphene materials. J Phys Chem C 113:13103–13107

    Article  CAS  Google Scholar 

  30. Hu Y, Guan C, Feng G, Ke Q, Huang X, Wang J (2015) Flexible asymmetric supercapacitor based on structure‐optimized Mn3O4/Reduced graphene oxide nanohybrid paper with high energy and power density. Adv Funct Mater 25:7291–7299

    Article  CAS  Google Scholar 

  31. Jeffery AA, Rao SR, Rajamathi M (2017) Preparation of MoS2–reduced graphene oxide (rGO) hybrid paper for catalytic applications by simple exfoliation–costacking. Carbon 112:8–16

    Article  CAS  Google Scholar 

  32. Zhang X-J, Wang G-S, Cao W-Q, Wei Y-Z, Liang J-F, Guo L, Cao M-S (2014) Enhanced microwave absorption property of reduced graphene oxide (RGO)-MnFe2O4 nanocomposites and polyvinylidene fluoride. ACS Appl Mater interfaces 6:7471–7478

    Article  CAS  Google Scholar 

  33. Wang W, Cai K, Wu X, Shao X, Yang X (2017) A novel poly(m-phenylenediamine)/reduced graphene oxide/nickel ferrite magnetic adsorbent with excellent removal ability of dyes and Cr(VI). J Alloy Compds 722:532–543

    Article  CAS  Google Scholar 

  34. Deshmukh K, Ahamed MB, Sadasivuni KK, Ponnamma D, Deshmukh RR, Pasha SK, AlMaadeed MA, Chidambaram K (2016) Graphene oxide reinforced polyvinyl alcohol/polyethylene glycol blend composites as high-performance dielectric material. J Polym Res 23:159

    Article  Google Scholar 

  35. Xiong P, Huang H, Wang X (2014) Design and synthesis of ternary cobalt ferrite/ graphene/polyaniline hierarchical nanocomposites for high-performance supercapacitors. J Power Sources 245:937–946

    Article  CAS  Google Scholar 

  36. Ma G, Chen Y, Li L, Jiang D, Qiao R, Zhu Y (2014) An attractive photocatalytic inorganic antibacterial agent: preparation and property of graphene/zinc ferrite/ polyaniline composites. Mater Lett 131:38–41

    Article  CAS  Google Scholar 

  37. Sankar KV, Selvan RK (2015) The ternary MnFe2O4/graphene/polyaniline hybrid composite as negative electrode for supercapacitors. J Power Sources 275:399–407

    Article  CAS  Google Scholar 

  38. Feng J, Hou Y, Wang X, Quan W, Li L (2016) In-depth study on adsorption and photocatalytic performance of novel reduced graphene oxide-ZnFe2O4-polyaniline composites. J Alloy Compd 681:157–166

    Article  CAS  Google Scholar 

  39. Vijaya Sankar K, Kalai R (2016) Selvan, Fabrication of flexible fiber supercapacitor using covalently grafted CoFe2O4/reduced graphene oxide/polyaniline and its electrochemical performances. Electrochim Acta 213:469–481

    Article  CAS  Google Scholar 

  40. Mousa MA, Khairy M, Shehab M (2017) Nanostructured ferrite/graphene/polyaniline using for supercapacitor to enhance the capacitive behavior. J Solid State Electrochem 21:995–1005

    Article  CAS  Google Scholar 

  41. Kooti M, Sedeh AN, Gheisari K, Figuerola A (2021) Synthesis, characterization, and performance of nanocomposites containing reduced graphene oxide, polyaniline, and cobalt ferrite. Phys B: Condens Matter 612:412974

    Article  CAS  Google Scholar 

  42. Hummers SW, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339

    Article  CAS  Google Scholar 

  43. Chougulea MA, Pawara SG, Godsea PR, Mulika RN, Senb S, Patil VB (2011) Synthesis and Characterization of Polypyrrole (PPy) Thin Films. Soft Nanosci Lett 1:6–10

    Article  Google Scholar 

  44. Nakajima T, Mabuchi A, Hagiwara R (1988) A new structure model of graphite oxide. Carbon 26:357–361

    Article  CAS  Google Scholar 

  45. Johra FT, Lee J, Jung W (2014) Facile and safe graphene preparation on solution based platform. J Ind Eng Chem 20:2883–2887

    Article  CAS  Google Scholar 

  46. Aigbe UO, Das R, Ho WH, Srinivasu V, Maity A (2018) A novel method for removal of Cr(VI) using polypyrrole magnetic nanocomposite in the presence of unsteady magnetic fields. Sep Purif Technol 194:377–387

    Article  CAS  Google Scholar 

  47. Seo I, Pyo M, Cho G (2002) Micrometer to nanometer patterns of polypyrrole thin films via microphase separation and molecular mask. Langmuir 18:7253–7257

    Article  CAS  Google Scholar 

  48. Liao Y, Li X-G, Kaner RB (2010) Facile synthesis of water-dispersible conducting polymer nanospheres. ACS Nano 4:5193–5202

    Article  CAS  Google Scholar 

  49. Fan W, Zhang C, Tjiu WW, Pramoda KP, He C, Liu T (2013) Graphene-wrapped polyaniline hollow spheres as novel hybrid electrode materials for supercapacitor applications. ACS Appl Mater Interfaces 5:3382–3391

    Article  CAS  Google Scholar 

  50. Jiang L, Dong C, Jin B, Wen Z, Jiang Q (2019) ZnFe2O4@PPy core-shell structure for high-rate lithium-ion storage. J Electroanal Chem 851:113442

    Article  CAS  Google Scholar 

  51. Gabal MA, Abou Zeid KM, El-Gendy AA, El-Shall MS (2019) One-step novel synthesis of CoFe2O4/graphene composites for organic dye removal. J Sol-gel Sci Technol 89:743–753

    Article  CAS  Google Scholar 

  52. Waldron RD (1955) Infrared spectra of ferrites. Phys Rev 99:1727–1735

    Article  CAS  Google Scholar 

  53. Li D, Muller MB, Gilje S, Kaner RB, Wallace G (2008) Processable aqueous dispersions of graphene nanosheets. Nat Nanotechnol 3:101–105

    Article  CAS  Google Scholar 

  54. Shanthala VS, Shobha Devi SN, Murugendrappa MV (2017) Synthesis, characterization and DC conductivity studies of polypyrrole/copper zinc iron oxide nanocomposites. J Asian Ceram Soc 5:227–234

    Article  Google Scholar 

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Authors and Affiliations

  1. Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia

    M. A. Gabal, E. A. Al-Harthy & Y. M. Al Angari

  2. Chemistry Department, Faculty of Science, Benha University, Benha, Egypt

    M. A. Gabal & A. Awad

  3. Chemistry department, Faculty of Science, University of Jeddah, Jeddah, Kingdom of Saudi Arabia

    E. A. Al-Harthy & A. A. Al-Juaid

  4. Physics Department, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia

    Abdu Saeed

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  1. M. A. Gabal
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Gabal, M.A., Al-Harthy, E.A., Al Angari, Y.M. et al. Synthesis, characterization and electrical properties of polypyrrole/Mn0.8Zn0.2Fe2O4/GO ternary hybrid composites using spent Zn-C batteries. J Sol-Gel Sci Technol 105, 781–792 (2023). https://doi.org/10.1007/s10971-023-06053-6

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