Synthesis of Lithium Titanium Oxide (Li₄Ti₅O₁₂) through Sol-Gel Method and the Effect of Graphene Addition in Lithium-Ion Battery Anodes

Abstract:

Li₄Ti₅O₁₂ (lithium titanium oxide) or LTO is extensively utilized as active material in Li-ion battery anode mainly due to its zero strain properties and excellent lithium-ion intercalation/deintercalation reversibility with negligible volumetric change. However, LTO is still faced with low electronic conductivity problem, thus the addition of another material such as graphene is necessary to overcome. In this study, LTO was synthesized using sol-gel method with addition of Li varied from 35, 40 and 55 wt% which was controlled by addition of Li₂CO_3. XRD analysis was performed to investigate the crystal structure and phase characteristic of synthesized powder. The results revealed that LTO with addition of 55 wt% Li exhibited the highest purity of Li₄Ti₅O₁₂ phase of 97.7%. It was then added with 5 wt% of graphene. Two-coin cells of Li-ion batteries were made from LTO powders without and with graphene addition as active materials for anode and their electrochemical performances were analyzed. LTO without and with graphene show conductivity of 3.40710^-5 and 2.48810^-5 S/cm, while obtained specific capacity was about 140 mAH and 85 mAh, respectively. This would require further optimization for current experimental condition particularly on graphene addition.

• Periodical: Defect and Diffusion Forum (Volume 417)
• Pages: 227-240
• DOI: https://doi.org/10.4028/p-kjj8v8
• Online since: June 2022
• Authors: Fawwaz Taqi Abiyu, Retna Deca Pravitasari, Riesma Tasomara, Ade Utami Hapsari, Sri Rahayu, Damisih Damisih, Hanif Yuliani, Oka Pradipta Arjasa, Nendar Herdianto, Yelvia Deni, Anne Zulfia Syarial, Jarot Raharjo*
• Keywords: Graphene, Lithium-Ion Battery, LTO, Sol-Gel

References

[1] S.A. Firnadya, A.Z. Syahrial, A. Subhan, Enhancing battery performance by nano Si addition to Li4Ti5O12 as anode material on lithium-ion battery, Ionics (Kiel). 24 (2018) 1029–1037.

DOI: 10.1007/s11581-017-2284-6

[2] B. Zhao, R. Ran, M. Liu, Z. Shao, A comprehensive review of Li4Ti5O12-based electrodes for lithium-ion batteries: The latest advancements and future perspectives, Mater. Sci. Eng. R Reports. 98 (2015) 1–71.

DOI: 10.1016/j.mser.2015.10.001

[3] A. Mahmoudzadeh Andwari, A. Pesiridis, S. Rajoo, R. Martinez-Botas, V. Esfahanian, A review of Battery Electric Vehicle technology and readiness levels, Renew. Sustain. Energy Rev. 78 (2017) 414–430.

DOI: 10.1016/j.rser.2017.03.138

[4] N. Nitta, F. Wu, J.T. Lee, G. Yushin, Li-ion battery materials: Present and future, Mater. Today. 18 (2015) 252–264.

DOI: 10.1016/j.mattod.2014.10.040

[5] D.A.H. Hanaor, C.C. Sorrell, Review of the anatase to rutile phase transformation, J. Mater. Sci. 46 (2011) 855–874.

DOI: 10.1007/s10853-010-5113-0

[6] H. Liu, G. Wen, S. Bi, P. Gao, Enhanced rate performance of nanosized Li4Ti5O12/graphene composites as anode material by a solid state-assembly method, Electrochim. Acta. 171 (2015) 114–120.

DOI: 10.1016/j.electacta.2015.05.008

[7] P.W. Winowatan, S. Selwyn, B. Priyono, A.Z. Syahrial, Enhancing battery performance of Li4Ti5O12 nanorod synthesized by hydrothermal method with Sn addition as anode material for lithium-ion battery, J. King Saud Univ. - Eng. Sci. 33 (2021) 396–403.

DOI: 10.1016/j.jksues.2020.05.009

[8] A. Wei, W. Li, L. Zhang, B. Ren, X. Bai, Z. Liu, Enhanced electrochemical performance of a LTO/N-doped graphene composite as an anode material for Li-ion batteries, Solid State Ionics. 311 (2017) 98–104.

DOI: 10.1016/j.ssi.2017.09.017

[9] C. Zhang, Y. Zhang, J. Wang, D. Wang, D. He, Y. Xia, Li4Ti5O12 prepared by a modified citric acid solegel method for lithium-ion battery, J. Power Source. 236 (2013) 118–125.

DOI: 10.1016/j.jpowsour.2013.01.135

[10] X. Guo, Q. Zhang, X. Ding, Q. Shen, C. Wu, L. Zhang, H. Yang, Synthesis and application of several sol–gel-derived materials via sol–gel process combining with other technologies: a review, J. Sol-Gel Sci. Technol. 79 (2016) 328–358.

DOI: 10.1007/s10971-015-3935-6

[11] Y.M. Liza, R.C. Yasin, S.S. Maidani, R. Zainul, Gelation Sol- Gel Proces s Densification Ageing Drying, Pendidik. FMIPA Univ. Negeri Padang. (2018).

[12] A.Z. Syahrial, B. Priyono, A.H. Yuwono, E. Kartini, H. Jodi, Johansyah, Synthesis of lithium titanate (Li4Ti5O12) by addition of excess lithium carbonate (Li2CO3) in titanium dioxide (TiO2) xerogel, Int. J. Technol. 7 (2016) 392–400.

DOI: 10.14716/ijtech.v7i3.2890

[13] H.C. Lee, W.-W. Liu, S.-P. Chai, A.R. Mohamed, C.W. Lai, C.-S. Khe, C.H. Voon, U. Hashim, N.M.S. Hidayah, Synthesis of Single-layer Graphene: A Review of Recent Development, Procedia Chem. 19 (2016) 916–921.

DOI: 10.1016/j.proche.2016.03.135

[14] Y. Shi, J. Gao, H.D. Abruña, H. Liu, H. Li, J. Wang, Y. Wu, Rapid synthesis of Li4Ti5O12/graphene composite with superior rate capability by a microwave-assisted hydrothermal method, Nano Energy. 8 (2014) 297–304.

DOI: 10.1016/j.nanoen.2014.06.009

[15] Z. He, Z. Wang, F. Wu, H. Guo, X. Li, X. Xiong, Spherical Li 4Ti 5O 12 synthesized by spray drying from a different kind of solution, J. Alloys Compd. 540 (2012) 39–45.

DOI: 10.1016/j.jallcom.2012.06.044

[16] D. Yoshikawaa, Y. Kadomaa, J.-M. Kima, K. Uia, N. Kumagaia, N. Kitamurab, Y. Idemoto, property as negative electrode material for Li-ion batteries Spray-drying synthesized lithium-excess Li4+xTi5−xO12−ı and its electrochemical, Electrochim. Acta. 55 (2010) 1872–1879.

DOI: 10.1016/j.electacta.2009.10.082

[17] J.Y. Eom, Y.H. Cho, S.I. Kim, D. Han, D. Sohn, Improvements in the electrochemical performance of Li4Ti5O12-coated graphite anode materials for lithium-ion batteries by simple ball-milling, J. Alloys Compd. 723 (2017) 456–461.

DOI: 10.1016/j.jallcom.2017.06.210

[18] T.M. Zima, A. V. Kozlova, N.F. Uvarov, Hydrothermal treatment of layered sodium titanate nanostructures and their conversion to Li4Ti5O12, Mater. Today Proc. 31 (2020) 522–525.

DOI: 10.1016/j.matpr.2020.06.085

[19] J.S. Park, C.L. Margez, T.A. Greszler, Effect of Particle Size and Electronic Percolation on Low-Temperature Performance in Lithium Titanate-Based Batteries, ACS Omega. 4 (2019) 21048–21053.

DOI: 10.1021/acsomega.9b02393

[20] E. Pohjalainen, T. Rauhala, M. Valkeapää, J. Kallioinen, T. Kallio, Effect of Li4Ti5O12 particle size on the performance of lithium ion battery electrodes at high C-rates and low temperatures, J. Phys. Chem. C. 119 (2015) 2277–2283.

DOI: 10.1021/jp509428c

[21] J. Li, Shaojie; Mao, S. Li, J. Mao, The Influence of Different Types of Graphene on the Lithium Titanate Anode Materials of a Lithium Ion Battery.pdf, J. Electron. Mater. 47 (2018) 5410–5416.

DOI: 10.1007/s11664-018-6439-7

[22] Y. Shi, L. Wen, F. Li, H.M. Cheng, Nanosized Li4Ti5O12/graphene hybrid materials with low polarization for high rate lithium ion batteries, J. Power Sources. 196 (2011) 8610–8617.

DOI: 10.1016/j.jpowsour.2011.06.002

[23] M. Wall, The Raman Spectroscopy of Graphene and the Determination of Layer Thickness, Thermo Sci. (2011) 5.

[24] A. Subhan, F. Oemry, S.N. Khusna, E. Hastuti, Effects of activated carbon treatment on Li 4 Ti 5 O 12 anode material synthesis for lithium-ion batteries, Ionics (Kiel). 25 (2019) 1025–1034.

DOI: 10.1007/s11581-018-2633-0

[25] T. Kim, W. Choi, H.C. Shin, J.Y. Choi, J.M. Kim, M.S. Park, W.S. Yoon, Applications of voltammetry in lithium ion battery research, J. Electrochem. Sci. Technol. 11 (2020) 14–25.

DOI: 10.33961/jecst.2019.00619

[26] E. Simamora, J. Riady, B. Priyono, A.Z. Syahrial, Effect of Carbon Active Addition to Electrochemical Performance of Li4Ti5O12/SnO2 Composite Anode on Lithiumion Battery, J. Phys. Conf. Ser. 1494 (2020).

DOI: 10.1088/1742-6596/1494/1/012045

[27] Y. Hui, L. Cao, Z. Xu, J. Huang, H. Ouyang, J. Li, Mesoporous Li4Ti5O12 nanoparticles synthesized by a microwave-assisted hydrothermal method for high rate lithium-ion batteries, J. Electroanal. Chem. 763 (2016) 45–50.

DOI: 10.1016/j.jelechem.2015.12.042

[28] H. Yan, W. Yao, R. Fan, Y. Zhang, J. Luo, J. Xu, Mesoporous Hierarchical Structure of Li4Ti5O12/Graphene with High Electrochemical Performance in Lithium-Ion Batteries, ACS Sustain. Chem. Eng. 6 (2018) 11360–11366.

DOI: 10.1021/acssuschemeng.8b01211

[29] D. Sui, L. Si, C. Li, Y. Yang, Y. Zhang, W. Yan, A Comprehensive Review of Graphene-Based Anode Materials for Lithium-ion Capacitors, Chemistry (Easton). 3 (2021) 1215–1246.

DOI: 10.3390/chemistry3040089

[30] A.K. Rai, J. Gim, S.W. Kang, V. Mathew, L.T. Anh, J. Kang, J. Song, B.J. Paul, J. Kim, Improved electrochemical performance of Li 4Ti 5O 12 with a variable amount of graphene as a conductive agent for rechargeable lithium-ion batteries by solvothermal method, Mater. Chem. Phys. 136 (2012) 1044–1051.

DOI: 10.1016/j.matchemphys.2012.08.048

[31] C. Lu, X. Wang, X. Zhang, H. Peng, Y. Zhang, G. Wang, Z. Wang, G. Cao, N. Umirov, Z. Bakenov, Effect of graphene nanosheets on electrochemical performance of Li4Ti5O12 in lithium-ion capacitors, Ceram. Int. 43 (2017) 6554–6562.

DOI: 10.1016/j.ceramint.2017.02.083

[32] H.-H. Chang, T.-H. Ho, Y.-S. Su, Graphene-Enhanced Battery Components in Rechargeable Lithium-Ion and Lithium Metal Batteries, C. 7 (2021) 65.

DOI: 10.3390/c7030065