STUDY OF THE PROCESS OF OBTAINING A COMPOSITE MATERIAL "SPHERICAL GRAPHITE – Fe2O3"
Abstract
In this article, a study was conducted on the process of obtaining a composite material “spherical graphite – iron oxide”, with the aim of its further use as an anode material for lithium-ion batteries. The composite was obtained by depositing iron oxide nanoparticles on the surface of spherical graphite. The influence of the deposition process parameters on the physico-chemical properties of the composite has been studied. It was found that the following factors have a significant effect on the final properties of the composite: the nature of the precipitator, the density of graphite loading of the precipitation working solution, the aging time of the system, the ratio of di- and trivalent iron in solution. Solutions of ammonia and urea were studied as precipitators. In the case of using urea, the formation of iron oxide particles with smaller coherent scattering regions, that is, with smaller crystallite sizes, was noted. Amorphous Fe2O3 precipitates are more preferable in terms of using them as an anode material. With an increase in the loading density of the graphite deposition solution, an increase in the yield of iron oxide nanoparticles was observed, however, at loading densities above 15 g/l, large iron oxide aggregates were formed. With an increase in the aging time of the deposition system, an improvement in the distribution of iron oxide nanoparticles over the surface of spherical graphite and a decrease in nanoparticle aggregates were noted. An increase in the molar fraction of Fe2+ in the precipitation solution has a similar effect. Based on the experimental data obtained, the optimal modes of the iron oxide deposition process were determined. Under these conditions, a sample of spherical graphite coated with Fe2O3 nanoparticles with average particle sizes of 30-50 nm was obtained. The oxide content in the sample was 3.7%. Electrochemical studies of the lithium-ion battery layout have shown that spherical graphite modified with iron oxide shows a reversible capacity increased to 370 mA∙h/g and greater stability of work.
For citation:
Bratkov I.V., Ivanov A.D., Kolchin A.D., Savitskiy I.A. Study of the process of obtaining a composite material "spherical graphite – Fe2O3". ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 3. P. 127-134. DOI: 10.6060/ivkkt.20246703.7041.
References
Skundin A.M., Voronkov G.Ya. Chemical current sources: 210 years. M.: Pokoleniye. 2010. 352 p. (in Russian).
Menkin S. Golodnitsky D. Peled E. Artificial solid-electrolyte interphase (SEI) for improved cycleability and safety of lithiumion cells for EV applications. Electrochem. Commun. 2009. V. 11. N 9. P. 1789–1791. DOI: 10.1016/j.elecom.2009.07.019.
Luo Fei, Chu Geng, Xia Xiaoxiang, Liu Bonan, Zheng Jieyun, Li Junjie, Li Hong, Gua Changzhi, Chen Liquan. Thick Solid Electrolyte Interphase Grown on Silicon Nan-cones Anodes during Slow Cycling and Their Negative Ef-fects on Performance for Li-ion Batteries. Nanoscale. 2015. V. 7. N 17. P. 7651–7658.
Zhang Yi Di, Li Yi, Xia Xin Hui, Wang Xiu Li, Gu Chang Dong, Tu Jiang Ping. Highenergy cathode materi-als for Li-ion batteries: A review of recent developments. Sci. China Technol. Sci. 2015. V. 58. N 11. P. 1809–1828. DOI: 10.1007/s11431-015-5933-x.
Loeffler B.N. Bresser D. Passerini S. Copley M. Secondary Lithium-Ion Battery Anodes: From First Commercial Batteries to Recent Research Activities. Johnson Matthey Technol. Rev. 2015. V. 59. N 1. P. 34-44. DOI: 10.1595/205651314X685824.
Xu Wu, Wang Jiulin, Ding Fei, Chen Xilin, Nasybulin E, Zhangad Yaohui, Zhang Ji Guang. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 2014. V. 7. N 2. P. 513-537. DOI: 10.1039/C3EE40795K.
Choi S., Jung G., Kim J.E., Kim T., Suh K.S. Lithium Intercalated Graphite with Preformed Passivation Layer as Superior Anode for Lithium Ion Batteries. Appl. Surf. Sci. 2018. V. 455. P. 637-372. DOI: 10.1016/j.apsusc.2018.05.229.
Wu Y., Li Y.-F., Wang L.-Y., Bai Y.-J., Zhao Z.-Y., Yin L.-W., Li H. Enhancing the Liion storage performance of graphite anode material modified by LiAlO2. Electrochim. Acta. 2017. V. 235. P. 463–470. DOI: 10.1149/2.0351713jes.
Chang Chia-Chin, Chen Li-Chia, Hung Tai-Ying, Su Yuh-Fan, Su Huang-Kai, Lin Jarrn-Horng, Hu Chih-Wei. Saravanan Lakshmanan. Chen Tsan-Yao. Nano-sized Tin OxideModified Graphite Composite as Efficient An-ode Material for Lithium Ion Batteries. Int. J. Electrochem. Sci. 2018. V. 13. P. 11762–11776. DOI: 10.20964/2018.12.28.
Wang Y., Zheng H., Qu Q., Zhang L., Battaglia V.S., Zheng H. Enhancing electrochemical properties of graph-ite anode by using poly(methylmethacrylate)–poly(vinylidene fluoride) composite binder. Carbon. 2015. V. 92. P. 318–326. DOI: 10.1016/j.carbon.2015.04.084.
Sun X., Radovanovic P.V., Cui B. Advances in spinel Li4Ti5O12 anode materials for lithium-ion batteries. New J. Chem. 2015. V. 39. N 1. P. 38–63. DOI: 10.1039/C4NJ01390E.
Jiang J., Chen J., Dahn J.R. Comparison of the Reactions Between Li7/3Ti5/3O4 or LiC6 and Nonaqueous Sol-vents or Electrolytes Using Accelerating Rate Calorimetry. J. Electrochem. Soc. 2004. V. 151. N 12. P. A2082-A2087. DOI: 10.1149/1.1817698.
Ohzuku T., Ueda A., Yamamota N. Zero-Strain Insertion Material of Li[Li1∕3Ti5∕3]O4 for Rechargeable Lithium Cells. J. Electrochem. Soc. 1995. V. 142. N 5. P. 1431-1435. DOI: 10.1149/1.2048592.
Vikram Babu B., Vijaya Babu K., Tewodros Aregai G., Seeta Devi L., Madhavi Latha B., Sushma Reddi M., Samatha K., Veeraiah V. Structural and electrical proper-ties of Li4Ti5O12 anode material for lithium-ion batteries. Results Phys. 2018. V. 9. P. 284–289. DOI: 10.1016/j.rinp.2018.02.050.
Wolfenstine J., Lee U., Allen J.L. Electrical conductivity and rate-capability of Li4Ti5O12 as a function of heat-treatment atmosphere. J. Power Sources. 2006. V. 154. N 1. P. 287–289. DOI: 10.1016/j.jpowsour.2005.12.044.
Reddy M.V., Subba Rao G.V., Chowdari B.V.R. Metal Oxides and Oxysalts as Anode Materials for Li Ion Batter-ies. Chem. Rev. 2013. V. 113. P. 5364–5457. DOI: 10.1021/cr3001884.
Jiang Yu, Jiang Zhong-Jie, Yang Lufeng, Cheng Shuang, Liu Meilin. A High-Performance Anode for Lith-ium Ion Batteries: Fe3O4 Microspheres Encapsulated in Hollow Graphene Shells. J. Mater. Chem. A. 2015. V. 3. N 22. P. 5364–5457. DOI: 10.1039/C5TA01848J.
Pelegov D.V., Koshkina A.A., Pryakhina V.I., Gorshkov V.S. Efficiency Threshold of Carbon Layer Growth in Li4Ti5O12/C Composites. J. Electrochem. Soc. 2018. V. 166. N 3. P. A5019–A5024. DOI: 10.1149/2.0031903jes.
Yudina T.F., Blinichev V.N., Bratkov I.V., Gushchina T.V., Melnikov A.G. Study of the process of spheroidiza-tion of natural graphites. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2018. V. 61. N 9-10. P. 48-52 (in Russian). DOI: 10.6060/ivkkt.20186109-10.5883.
Bratkov I.V., Ivanov A.D., Kolchin A.D., Savitsky I.A., Smirnov N.N. Study of the influence of mechanochemical activation in an impact-reflective mill on the crystal structure of natural graphite. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 4. P. 68-74 (in Russian). DOI: 10.6060/ivkkt.20236604.6795.
