Investigations on conductivity of nitrogen-doped reduced graphene oxide/Li2FeSiO4 cathode material prepared by microwave-assisted method for lithium-ion batteries

Zomorrodi, Saba; Hoveida Marashi, Seyed Pirouz; Sadeghian, Zahra; Javadian, Soheila

doi:10.22060/ajme.2025.23280.6119

دانشگاه صنعتی امیرکبیر

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	Investigations on conductivity of nitrogen-doped reduced graphene oxide/Li2FeSiO4 cathode material prepared by microwave-assisted method for lithium-ion batteries
AUT Journal of Mechanical Engineering
دوره 9، شماره 2، 2025، صفحه 167-178 اصل مقاله (1.27 M)
نوع مقاله: Research Article
شناسه دیجیتال (DOI): 10.22060/ajme.2025.23280.6119
نویسندگان
Saba Zomorrodi¹؛ Seyed Pirouz Hoveida Marashi^* ¹؛ Zahra Sadeghian²؛ Soheila Javadian³
¹Department of Materials Science and Metallurgical Engineering, Amirkabir University of Technology, Tehran, Iran
²Research Institute of Petroleum Industry (RIPI), Tehran, Iran
³Faculty of Basic Science, Tarbiat Modares University, Tehran, Iran
چکیده
Li₂FeSi0₄ is a promising cathode active material for lithium-ion batteries due to its significant theoretical capacity (332 mAhg^-1). Nevertheless, its practical electrochemical performance faces significant hurdles due to low electron conductivity. In the research, a simple solid-state technique was used to synthesize the high-purity cathode material Li₂FeSi0₄. Additionally, nitrogen-doped reduced graphene oxide nanosheets were fabricated using a household microwave-assisted process and then selectively deposited to coat the active cathode material to increase conductivity and significantly improve electrocatalysis. The properties of the as-prepared nanosheets and Li₂FeSi0₄/ nitrogen-doped reduced graphene oxide nanocomposites are studied using X-ray diffraction, high-resolution transmission electron microscopy, field emission scanning electron microscopy, RAMAN spectrometry, and Fourier transform infrared spectroscopy techniques. The study investigated the influence of different amounts of as-prepared nanosheet coatings on the electrical conductivity of the Li₂FeSi0₄ by comparing their band gap energy value. Accordingly, a lower band gap, indicates higher and better electronic conductivity in the cathode of lithium-ion batteries. Therefore, diffusion reflectance spectroscopy and electrochemical impedance spectroscopy were used to determine the band gap size and conductivity. Studies show that coating Li₂FeSi0₄ particles with only 5 wt% nitrogen-doped nanosheets reduced the bandgap energy value by about 0.78 eV and increased the electrical conductivity by 54.31%. It is concluded that Li₂FeSi0₄/ nitrogen-doped reduced graphene oxide nanocomposites can be a promising candidate as a high-performance cathode material for lithium-ion batteries.
کلیدواژه‌ها
Lithium Iron Orthosilicate؛ Graphene Nanosheets؛ Solid-State Synthesis؛ Bandgap؛ LIBs

مراجع
[1] T.ZM. Bawm, A.R.Md. Harunur Rashid, M. Hasanuzzaman, Effects of Doping/Co-Doping on Li2FeSiO4 Cathode Material for Lithium-Ion Batteries: A Review, Encyclopedia of Materials: Electronics, 3 (2023) 381-391. [2] T. Muthu Muniyandi, S. Balamurugan, N. Naresh, I. Prakash, R. Venkatesh, U. Deshpande, N. Satyanarayana, Li2FeSiO4/C aerogel: A promising nanostructured cathode material for lithium-ion battery applications, Journal of Alloys and Compounds, 887 (2021) 161341. [3] X. Bi, L. Chang. Sh. Luo, Sh. Cao, A. Wei, W. Yang, J. Liu, F. Zhang, The recent progress of Li2FeSiO4 as a poly-anionic cathode material for lithium-ion batteries, Energe Reaserch, 46 (2021) 5373–5398. [4] F. Zheng, Q. Lin, S. Wu, Z.-z. Zhu, Influence of the Fe-Si-O framework in crystal structure on the phase stability and electrochemical performance of Li2FeSiO4 cathode, Solid State Ionics, 356 (2020) 115436. [5] H. Kageyama, Y. Hashimoto, Y. Oaki, H. Imai, Six-armed twin crystals composed of lithium iron silicate nanoplates and their electrochemical properties, CrystEngComm, 17(44) (2015) 8486-8491. [6] A. Nytén, A. Abouimrane, M. Armand, T. Gustafsson, J.O. Thomas, Electrochemical performance of Li2FeSiO4 as a new Li-battery cathode material, Electrochemistry communications, 7(2) (2005) 156-160. [7] X.B. Longjiao Chang, Shaohua Luo, Wei Yang, Anlu Wei, n Yang, Jianan Liu, Insight into the high-efficiency separation of Si element from low-grade laterite nickel ore and the preparation of Li2FeSiO4/C cathode materials for lithium-ion batteries, Journal of Alloys and Compounds, 937(168357) (2023). [8] H.C. Yutian Yang, Rihuang Nie, Cheng Li, Shuangwu Xu, Mengcheng Zhou, Xinyu Zhang, Hongming Zhou, Using the synergistic effect of co-doping to engineer magnesium and chlorine co-doping to improve the electrochemical performance of Li2FeSiO4/C cathodes, Journal of Alloys and Compounds, 935(167958) (2023). [9] S. Chakrabarti, A.K. Thakur, K. Biswas, Effect of Ti modification on Structural, Electronic and Electrochemical properties of Li 2 FeSiO 4 —A DFT study using FPLAPW approach, Electrochimica Acta, 236 (2017) 288-296. [10] H. Li, Y. Li, X. Cheng, C. Gong, Hollow Hemispherical Lithium Iron Silicate Synthesized by an Ascorbic Acid-Assisted Hydrothermal Method as a Cathode Material for Li Ion Batteries, Materials (Basel), 15(10) (2022). [11] S. Yi, J. Moon, M. Cho, K. Cho, Ab-initio design of novel cathode material LiFeP1-SiO4 for rechargeable Li-ion batteries, Electrochimica Acta, 313 (2019) 70-78. [12] Y.L. Xiaoying Luo, Xuan Cheng, Mechanistic study in sulfur-carbon co-modification on Li2FeSiO4 for lithium-ion batteries, Ceramics International, 49 (2023) 27277–27287. [13] H. Qiu, D. Jin, C. Wang, G. Chen, L. Wang, H. Yue, D. Zhang, Design of Li2FeSiO4 cathode material for enhanced lithium-ion storage performance, Chemical Engineering Journal, 379 (2020) 122329. [14] K. Pushnitsa, P. Novikov, A. Popovich, Q. Wang, Synthesis of Li2FeSiO4/C composite cathode material for Li-ion batteries and influence of dispersion effect on electrochemical characteristics, Materials Today: Proceedings, 30 (2020) 773-777. [15] P. Vajeeston, Ionic conductivity enhancement by particle size reduction in Li2FeSiO4, Materials Letters, 218 (2018) 313-316. [16] B. Shen, J. Zeng, N. Fu, X. Wang, Zh. Yong, High reversible capacity silicon anode by segregated graphene-carbon nanotube networks for lithium ion half/full batteries, Energy Storage, 55 (2022) 105767. [17] T. Liu, Y. Liu, Y. Yu, Y. Ren, C. Sun, Y. Liu, J. Xu, C. Liu, Z. Yang, W. Lu, P. Ferreira, Z. Chao, J. Xie, Approaching theoretical specific capacity of iron-rich lithium iron silicate using graphene-incorporation and fluorine-doping, Journal of Materials Chemistry A, 10(8) (2022) 4006-4014. [18] W. Zhang, W. Shao, B. Zhao, K. Dai, Review—Research Progress of Li2FeSiO4 Cathode Materials for Lithium-Ion Batteries, Journal of The Electrochemical Society, 169(7) (2022) 070526. [19] J. Yang, X. Kang, D. He, A. Zheng, M. Pan, S. Mu, Graphene activated 3D-hierarchical flower-like Li2FeSiO4 for high-performance lithium-ion batteries, Journal of Materials Chemistry A, 3(32) (2015) 16567-16573. [20] J. Yang, L. Hu, J. Zheng, D. He, L. Tian, Sh. Mu, F. Pan, Li2FeSiO4 nanorods bonded with graphene for high-performance batteries, Materials Chemistry A, 3 (2015) 9601–9608. [21] L.L. Zhang, S. Duan, X.L. Yang, G. Peng, G. Liang, Y.H. Huang, Y. Jiang, S.B. Ni, M. Li, Reduced graphene oxide modified Li2FeSiO4/C composite with enhanced electrochemical performance as cathode material for lithium-ion batteries, ACS Appl Mater Interfaces, 5(23) (2013) 12304-12309. [22] Y. Shang, H. Xu, M. Li, G. Zhang, Preparation of N-Doped Graphene by Hydrothermal Method and Interpretation of N-Doped Mechanism, Nano, 12(02) (2017) 1750018. [23] X. Wang, C. Qing, Q. Zhang, W. Fan, X. Huang, B. Yang, J. Cui, Facile synthesis and enhanced electrochemical performance of Li2FeSiO4/C/reduced graphene oxide nanocomposites, Electrochimica Acta, 134 (2014) 371-376. [24] Z. Liu, Q. Wang, B. Zhang, T. Wu, Y. Li, Efficient Removal of Bisphenol A Using Nitrogen-Doped Graphene-Like Plates from Green Petroleum Coke, Molecules, 25(15) (2020) 3543. [25] D.R.A.B. Alyaa. K. Mageed, A. Salmiaton, Shamsul Izhar, Musab Abdul Razak, H.M.Yusoff, F.M. Yasin, Suryani Kamarudin, Preparation and Characterization of Nitrogen Doped Reduced Graphene Oxide Sheet, nternational Journal of Applied Chemistry, 12 (2016) 104-108. [26] H. Aghajani, A.T. Tabrizi, R. Ghorbani, S. Behrangi, M. Stupavska, N. Abdian, Evaluation of electrochemical hydrogen storage capability of three-dimensional nano-structured nitrogen-doped graphene, Journal of Alloys and Compounds, 906 (2022) 164284. [27] X.D. H. Gao, Q. Wu, Z. Gao, Sh. Lou, Y. Zhao, Improved capacity and cycling stability of Li2FeSiO4 nanocrystalline induced by nitrogen-doped carbon coating, Solid State Electrochemistry, 25 (2021) 1679–1689. [28] H. Gao, Q. Wu, M. Guo, S. Yang, Y. Zhao, Y.-U. Kwon, Rationally fabricating nitrogen-doped carbon coated nanocrystalline Li2FeSiO4@N-C with excellent Li-ion battery performances, Electrochimica Acta, 318 (2019) 720-729. [29] Z. Dong Peng, Y. Bing Cao, G. Rong Hu, K. Du, X. Guang Gao, Z. Wei Xiao, Microwave synthesis of Li2FeSiO4 cathode materials for lithium-ion batteries, Chinese Chemical Letters, 20(8) (2009) 1000-1004. [30] M. Rahsepar, F. Foroughi, H. Kim, A new enzyme-free biosensor based on nitrogen-doped graphene with high sensing performance for electrochemical detection of glucose at biological pH value, Sensors and Actuators B: Chemical, 282 (2019) 322-330. [31] Y. Zeng, H.-C. Chiu, M. Rasool, N. Brodusch, R. Gauvin, D.-T. Jiang, D.H. Ryan, K. Zaghib, G.P. Demopoulos, Hydrothermal crystallization of Pmn21 Li2FeSiO4 hollow mesocrystals for Li-ion cathode application, Chemical Engineering Journal, 359 (2019) 1592-1602. [32] X. Lu, H.-C. Chiu, Z. Arthur, J. Zhou, J. Wang, N. Chen, D.-T. Jiang, K. Zaghib, G.P. Demopoulos, Li-ion storage dynamics in metastable nanostructured Li2FeSiO4 cathode: Antisite-induced phase transition and lattice oxygen participation, Journal of Power Sources, 329 (2016) 355-363. [33] T. Masese, C. Tassel, Y. Orikasa, Y. Koyama, H. Arai, N. Hayashi, J. Kim, T. Mori, K. Yamamoto, Y. Kobayashi, H. Kageyama, Z. Ogumi, Y. Uchimoto, Crystal Structural Changes and Charge Compensation Mechanism during Two Lithium Extraction/Insertion between Li2FeSiO4 and FeSiO4, The Journal of Physical Chemistry C, 119(19) (2015) 10206-10211. [34] S. Emami, H. Aghajani, A.T. Tabrizi, Sustainable Oxygen-Free Copper Powder Production Method from Wastes, Journal of Sustainable Metallurgy, 9(4) (2023) 1803-1809. [35] H. Qiu, H. Yue, T. Zhang, Y. Ju, Y. Zhang, Z. Guo, C. Wang, G. Chen, Y. Wei, D. Zhang, Enhanced Electrochemical Performance of Li 2 FeSiO 4 /C Positive Electrodes for Lithium-Ion Batteries via Yttrium Doping, Electrochimica Acta, 188 (2016) 636-644. [36] R. Tan, J. Yang, J. Zheng, K. Wang, L. Lin, S. Ji, J. Liu, F. Pan, Fast rechargeable all-solid-state lithium ion batteries with high capacity based on nano-sized Li2FeSiO4 cathode by tuning temperature, Nano Energy, 16 (2015) 112-121. [37] L. Liu, P. Wang, J. Li, G. Shi, L. Ma, J. Zhao, H. An, Hydrothermal preparation and intrinsic transport properties of nanoscale Li2FeSiO4, Solid State Ionics, 320 (2018) 353-359. [38] P. Sivaraj, B. Nalini, K.P. Abhilash, D. Lakshmi, P. Christopher Selvin, P. Balraju, Study on the influences of calcination temperature on structure and its electrochemical performance of Li2FeSiO4/C nano cathode for Lithium Ion Batteries, Journal of Alloys and Compounds, 740 (2018) 1116-1124. [39] J. Yang, J. Zheng, X. Kang, G. Teng, L. Hu, R. Tan, K. Wang, X. Song, M. Xu, S. Mu, F. Pan, Tuning structural stability and lithium-storage properties by d -orbital hybridization substitution in full tetrahedron Li 2 FeSiO 4 nanocrystal, Nano Energy, 20 (2016) 117-125. [40] L.-L. Zhang, H.-B. Sun, X.-L. Yang, Y.-W. Wen, Y.-H. Huang, M. Li, G. Peng, H.-C. Tao, S.-B. Ni, G. Liang, Study on electrochemical performance and mechanism of V-doped Li2FeSiO4 cathode material for Li-ion batteries, Electrochimica Acta, 152 (2015) 496-504. [41] Y. Zeng, H.-C. Chiu, B. Ouyang, K. Zaghib, G.P. Demopoulos, Defect Engineering of Iron-Rich Orthosilicate Cathode Materials with Enhanced Lithium-Ion Intercalation Capacity and Kinetics, ACS Applied Energy Materials, 3(1) (2019) 675-686. [42] L. Li, E. Han, M. Jiao, Y. Zhang, X. Yang, W. Yuan, The effect of Ag or Zn composite on the electrochemical performance of Li2FeSiO4 cathode materials, Ionics, 26(6) (2020) 2727-2736.
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Investigations on conductivity of nitrogen-doped reduced graphene oxide/Li2FeSiO4 cathode material prepared by microwave-assisted method for lithium-ion batteries