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Self-propagating synthesis of nitrogen-doped graphene as supercapacitor electrode materials

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Abstract

Doping heteroatoms into graphene is effective to open the energy bandgap and increase the free carrier density, thereby improving its electronic and electrochemical properties. In this paper, CO was selected as the carbon source for the preparation of graphene through the self-propagating reaction. During the reaction, a variety of hexamethyltetramine were used to dope N atoms into the graphene when different ratios of MgO/Mg were compared. Microstructural and electrochemical characterizations were conducted to study the effects of nitrogen doping as well as MgO/Mg ratio on the performance of the graphene as supercapacitor electrode. The Raman spectra show the presence of graphene after self-propagating reaction. The graphene doped from hexamethyltetramine shows the existence of pyridinic-N, pyrrolic-N, and graphitic-N. In general, the percentages of pyridinic-N in the materials increased with the usage of hexamethyltetramine. Given the same condition, the pyridinic-N content of the samples based on MgO/Mg ratio of 8 was higher than that of the samples using MgO/Mg ratio of 4. Besides, the specific surface areas of the samples increase as MgO/Mg increased. The introduction of nitrogen atoms in the graphene increased the active sites on its surface and consequently, the specific capacity, capacity retention rate and energy density of the supercapacitor. At the current density of 1Ag−1, the specific capacity of N-SHS-8-3 was 153 Fg−1 and the capacity retention rate was 60% as the current density increased to 20Ag−1.

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References

  1. K. Poonam, A. Sharma, S.K. Arora, Tripathi, review of supercapacitors: materials and devices. J. Energy Storage 21, 801 (2019)

    Article  Google Scholar 

  2. A.G. Pandolfo, A.F. Hollenkamp, Carbon properties and their role in supercapacitors. J. Power Sources 157, 11 (2006)

    Article  CAS  Google Scholar 

  3. L. Gu, S. Liu, H.C. Zhao, H.B. Yu, Facile preparation of water-dispersible graphene sheets stabilized by carboxylated oligoanilines and their anticorrosion coatings. ACS Appl. Mater. Interfaces 7, 17641 (2015)

    Article  CAS  Google Scholar 

  4. H.C. Deng, M.W. Zhu, T.X. Jin, C.H. Cheng, J.G. Zheng, Y. Qian, One-step synthesis of nitrogen, sulphur-codoped graphene as electrode material for supercapacitor with excellent cycling stability. Int. J. Electrochem. Sci. 15, 16 (2020)

    Article  CAS  Google Scholar 

  5. Y.S. Bai, L.D. Lu, J.C. Bao, G.X. Sun, B.B. Zhang, J.P. Zeng, S. Chen, The preparation and electrochemical performance of nitrogen-doped graphene/Co(OH)(2) composite. Int. J. Electrochem. Sci. 14, 606 (2019)

    Article  CAS  Google Scholar 

  6. Z. Zapata-Benabithe, F. Carrasco-Marin, C. Moreno-Castilla, Preparation, surface characteristics, and electrochemical double-layer capacitance of KOH-activated carbon aerogels and their O- and N-doped derivatives. J. Power Sources 219, 80 (2012)

    Article  CAS  Google Scholar 

  7. V. Singh, D. Joung, L. Zhai, S. Das, S.I. Khondaker, S. Seal, Graphene based materials: past, present and future. Prog. Mater. Sci. 56, 1178 (2011)

    Article  CAS  Google Scholar 

  8. H.M. Jeong, J.W. Lee, W.H. Shin, Y.J. Choi, H.J. Shin, J.K. Kang, J.W. Choi, Nitrogen-doped graphene for high-performance ultracapacitors and the importance of nitrogen-doped sites at basal planes. Nano Lett. 11, 2472 (2011)

    Article  CAS  Google Scholar 

  9. Z.Y. Xing, B. Wang, W.Y. Gao, C.Q. Pan, J.K. Halsted, E.S. Chong, J. Lu, X.F. Wang, W. Luo, C.H. Chang, Y.H. Wen, S.Q. Ma, K. Amine, X.L. Ji, Reducing CO2 to dense nanoporous graphene by Mg/Zn for high power electrochemical capacitors. Nano Energy 11, 600 (2015)

    Article  CAS  Google Scholar 

  10. D. Herath, T. Dinadayalane, Computational investigation of double nitrogen doping on graphene. J. Mol. Model. (2018). https://doi.org/10.1007/s00894-017-3560-0

    Article  Google Scholar 

  11. T. Granzier-Nakajima, K. Fujisawa, V. Anil, M. Terrones, Y.T. Yeh, Controlling nitrogen doping in graphene with atomic precision: synthesis and characterization. Nanomaterials (2019). https://doi.org/10.3390/nano9030425

    Article  Google Scholar 

  12. X.X. He, Z. Tang, L.L. Gao, F.Y. Wang, J.P. Zhao, Z.C. Miao, X.Z. Wu, J. Zhou, Y. Su, S.P. Zhuo, Facile and controllable synthesis N-doping porous Graphene for high-performance Supercapacitor. J. Electroanal. Chem. (2020). https://doi.org/10.1016/j.jelechem.2020.114311

    Article  Google Scholar 

  13. R. Dubey, V. Guruviah, Review of carbon-based electrode materials for supercapacitor energy storage. Ionics 25, 1419 (2019)

    Article  CAS  Google Scholar 

  14. Z.Y. Wei, Q. Zhao, M.Y. He, S.L. Su, Y. Tian, C.D. Wang, S.J. Li, D.H. Ping, B. Jing, G.J. Hu, Self-propagating high-temperature synthesis of porous graphene by magnesiothermic reaction as high-performance electrochemical electrode material. J. Alloys Compds. (2022). https://doi.org/10.1016/j.jallcom.2021.163552

    Article  Google Scholar 

  15. J. Cheng, J.Q. Ma, J. Chen, H. Tan, Q.C. Sun, J. Yang, Self-propagating high-temperature synthesis of multi-layer graphene. Mater. Lett. (2020). https://doi.org/10.1016/j.matlet.2019.127213

    Article  Google Scholar 

  16. A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri, S. Piscanec, D. Jiang, K.S. Novoselov, S. Roth, A.K. Geim, Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. (2006). https://doi.org/10.1103/PhysRevLett.97.187401

    Article  Google Scholar 

  17. A.L.M. Reddy, A. Srivastava, S.R. Gowda, H. Gullapalli, M. Dubey, P.M. Ajayan, Synthesis of nitrogen-doped graphene films for lithium battery application. ACS Nano 4, 6337 (2010)

    Article  CAS  Google Scholar 

  18. Y. Gao, L.Q. Liu, S.Z. Zu, K. Peng, D. Zhou, B.H. Han, Z. Zhang, The effect of inter layer adhesion on the mechanical behaviors of macroscopic graphene oxide papers. ACS Nano 5, 2134 (2011)

    Article  CAS  Google Scholar 

  19. A. Gupta, G. Chen, P. Joshi, S. Tadigadapa, P.C. Eklund, Raman scattering from high-frequency phonons in supported n-graphene layer films. Nano Lett. 6, 2667 (2006)

    Article  CAS  Google Scholar 

  20. T.M.G. Mohiuddin, A. Lombardo, R.R. Nair, A. Bonetti, G. Savini, R. Jalil, N. Bonini, D.M. Basko, C. Galiotis, N. Marzari, K.S. Novoselov, A.K. Geim, A.C. Ferrari, Uniaxial strain in graphene by Raman spectroscopy: G peak splitting, Gruneisen parameters, and sample orientation. Phys. Rev. 79(20), 205433 (2009)

    Article  Google Scholar 

  21. B. SanthiBhushan, M.S. Khan, V.K. Bohat, A. Srivastava, Quantum Capacitance estimations of pyrrolic-rich graphene for supercapacitor electrodes. IEEE Trans. Nanotechnol. 17, 205 (2018)

    Article  CAS  Google Scholar 

  22. X. Wang, Y. Ding, H. Lu, F. Chen, N. Zhang, M. Ma, Chemoselective solution synthesis of pyrazolic-structure-rich nitrogen-doped graphene for supercapacitors and electrocatalysis. Chem. Eng. J. 347, 754 (2018)

    Article  CAS  Google Scholar 

  23. F.N. Indah Sari, J.-M. Ting, High performance asymmetric supercapacitor having novel 3D networked polypyrrole nanotube/N-doped graphene negative electrode and core-shelled MoO3/PPy supported MoS2 positive electrode. Electrochim. Acta (2019). https://doi.org/10.1016/j.electacta.2019.07.044

    Article  Google Scholar 

  24. L. Xie, C. Tang, Z. Bi, M. Song, Y. Fan, C. Yan, X. Li, F. Su, Q. Zhang, C. Chen, Hard carbon anodes for next-generation Li-Ion batteries: review and perspective. Adv. Energy Mater. 11, 2101650 (2021)

    Article  CAS  Google Scholar 

  25. Y. Ding, S. Huang, Y. Sun, Y. Li, L. Zhu, S. Wang, Preparation of nitrogen and sulfur co-doped and interconnected hierarchical porous biochar by pyrolysis of mantis shrimp in CO2 atmosphere for symmetric supercapacitors. ChemElectroChem 8, 3745 (2021)

    Article  CAS  Google Scholar 

  26. S. Nathabumroong, N. Chanlek, T. Sareein, E. Chongsereecharoen, P. Pakawanit, C. Poochai, T. Eknapakul, C. Sriprachuabwong, H. Nakajima, P. Thangdee, T. Lomas, S. Rujirawat, P. Songsiriritthigul, P. Manyum, A. Tuantranont, R. Yimnirun, Comparative study on the structural and electrochemical properties of nitrogen-doped and nitrogen and sulfur co-doped reduced graphene oxide electrode prepared by hydrothermal technique. Radiat. Phys. Chem. (2023). https://doi.org/10.1016/j.radphyschem.2023.110887

    Article  Google Scholar 

  27. L. Ji, B. Wang, Y. Yu, N. Wang, J. Zhao, N, S co-doped biomass derived carbon with sheet-like microstructures for supercapacitors. Electrochim. Acta. (2020). https://doi.org/10.1016/j.electacta.2019.135348

    Article  Google Scholar 

  28. S. Nathabumroong, C. Poochai, N. Chanlek, T. Eknapakul, S. Sonsupap, W. Tuichai, C. Sriprachuabwong, S. Rujirawat, P. Songsiriritthigul, A. Tuantranont, R. Yimnirun, Enhanced surface and electrochemical properties of nitrogen-doped reduced graphene oxide by violet laser treatment for high charge storage and lower self-discharge supercapacitors. J. Power Sources (2021). https://doi.org/10.1016/j.jpowsour.2021.230517

    Article  Google Scholar 

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Funding

This work was financially supported by the National Natural Science Foundation of China (Grant No. 21875283).

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Authors and Affiliations

  1. School of Mechanical and Electrical Engineering, China University of Mining and Technology (Beijing), D11 Xue Yuan Lu, Beijing, 100083, People’s Republic of China

    Lin Liu, Xi Dong, Chuanjian Jiang & Xiye Xu

  2. Research Institute of Chemical Defense, Beijing, China

    Xi Dong, Chuanjian Jiang, Xiye Xu, Rixin Lai & Wenfeng Zhang

  3. Beijing Key Laboratory of Advanced Chemical Energy Storage Technology and Materials, Beijing, People’s Republic of China

    Rixin Lai & Wenfeng Zhang

Authors
  1. Lin Liu
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  2. Xi Dong
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  3. Chuanjian Jiang
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Contributions

All authors contributed to the study conception and design. The first draft of the manuscript was written by LL, XD and XX. All authors read and approved the final manuscript. Conceptualization: LL; Methodology: CJ and RL; Formal analysis and investigation: XD and CJ; Writing—original draft preparation: XD and XX; Writing—review and editing: LL; Funding acquisition: WZ.

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Correspondence to Lin Liu.

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Liu, L., Dong, X., Jiang, C. et al. Self-propagating synthesis of nitrogen-doped graphene as supercapacitor electrode materials. J Mater Sci: Mater Electron 34, 1363 (2023). https://doi.org/10.1007/s10854-023-10758-3

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