THE DENSITY FUNCTIONAL THEORY STUDY OF Li-ION DIFFUSION IN Na-DOPED Li4Ti5O12 AS LITHIUM-ION BATTERY ANODE

Achda Fitriah; Anugrah Azhar; Adam Badra Cahaya; Edi Suprayoga; Muhammad Aziz Majidi

doi:10.21009/SPEKTRA.073.04

Authors

Achda Fitriah Department of Physics, Faculty of Mathematics and Natural Sciences, University of Indonesia, Depok 16424, Indonesia
Anugrah Azhar Physics Study Program, Faculty of Sciences and Technology, Syarif Hidayatullah State Islamic University Jakarta, South Tangerang 15412, Indonesia
Adam Badra Cahaya Department of Physics, Faculty of Mathematics and Natural Sciences, University of Indonesia, Depok 16424, Indonesia
Edi Suprayoga Research Center for Quantum Physics, National Research and Innovation Agency (BRIN), South Tangerang 15214, Indonesia
Muhammad Aziz Majidi Department of Physics, Faculty of Mathematics and Natural Sciences, University of Indonesia, Depok 16424, Indonesia

DOI:

https://doi.org/10.21009/SPEKTRA.073.04

Keywords:

lithium-ion battery, lithium titanate, Li-ion diffusion, DFT

Abstract

Spinel phase lithium titanate (Li₄Ti₅O₁₂ or LTO) has been studied as an alternative anode material with a “zero-strain” characteristic structure to improve safety, cycling stability, and rate performance. LTO offers stable Li-ion diffusion at a higher charge-discharge rate without noticeable structural change. However, LTO exhibits low electronic conductivity and low Li-ion diffusion compared to graphite-based anode materials, limiting its rate capability. In this study, we investigate the impact of Na atom doping on the diffusion rate in the Li₄Ti₅O₁₂ (LTO) spinel phase using the density functional theory (DFT). Based on the nudged elastic band (NEB) calculation, we obtain the energy barrier values and each diffusion pathway, with barrier energy varying about 0.3~0.4 eV and affecting the value of the diffusion constant obtained. The study reveals the role of Na atom doping in the lithium-ion diffusion in Na_xLi_4-xTi₅O₁₂ for battery anode material.

References

[1] M. A. Hannan et al., “A review of lithium-ion battery state of charge estimation and management system in electric vehicle applications: Challenges and recommendations,” Renewable and Sustainable Energy Reviews, vol. 78, 2017, doi: 10.1016/j.rser.2017.05.001.
[2] A. Tomaszewska et al., “Lithium-ion battery fast charging: A review,” Publisher Full Text, e-Transportation, vol. 1, 2019, doi: 10.1016/j.etran.2019.100011.
[3] B. Ziebarth, et al., “Lithium diffusion in the spinel phase Li4Ti5O12 and in the rocksalt phase Li7Ti5O12 of lithium titanate from first principles,” Phys. Rev. B - Condens. Matter Mater. Phys., vol. 89, no. 17, 2014, doi: 10.1103/PhysRevB.89.174301.
[4] K. Tada, et al., “A comparative study of Na3LiTi5O12 and Li4Ti5O12: Geometric and electronic structures obtained by density functional theory calculations,” Chemical Physics Letters, vol. 731, 2019, doi: 10.1016/j.cplett.2019.136598.
[5] A. Van der Ven and G. Ceder, “Lithium diffusion mechanisms in layered intercalation compounds,” in Journal of Power Sources, vol. 97-98, 2001, doi: 10.1016/S0378-7753(01)00638-3.
[6] M. Wilkening et al., “Microscopic Li self-diffusion parameters in the lithiated anode material Li4+xTi5O12 (0 ≤ x ≤ 3) measured by 7Li solid state NMR,” Phys. Chem. Chem. Phys, vol. 9, no. 47, 2007, doi: 10.1039/b713311a.
[7] L. Zhang et al., “Enhancing the electrochemical performance of Li4Ti5O12 anode materials by codoping with Na and Br,” Journal of Alloys and Compounds, vol. 903, 2022, doi: 10.1016/j.jallcom.2022.163962.
[8] S. Loftager et al., “A Density Functional Theory Study of the Ionic and Electronic Transport Mechanisms in LiFeBO3 Battery Electrodes,” The Journal of Physical Chemistry, vol. 120, no. 33, 2016, doi: 10.1021/acs.jpcc.6b03456.
[9] Berkeley Lab, “The Materials Project is powered by open-source software, mp-685194: Li4Ti5O12 (monoclinic, C2/c, 15),” https://materialsproject.org/materials/mp-685194/.
[10] K. Kataoka et al., “Single crystal growth and structure refinement of Li4Ti5O12,” J. Phys. Chem. Solids, vol. 69, no. 5, pp. 1454-1456, 2007, doi: 10.1016/j.jpcs.2007.10.134.
[11] K. Momma and F. Izumi, “VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data,” J. Appl. Crystallogr, vol. 44, no. 6, 2011, doi: 10.1107/S0021889811038970.
[12] P. Giannozzi et al., “QUANTUM ESPRESSO: A modular and open-source software project for quantum simulations of materials,” J. Phys. Condens. Matter, vol. 21, no. 39, 2009, doi: 10.1088/0953-8984/21/39/395502.
[13] M. Ernzerhof et al., “Coupling-constant dependence of atomization energies,” Int. J. Quantum Chemistry, vol. 64, no. 3, pp. 285-295, 1997, doi: 10.1002/(SICI)1097-461X(1997)64:3<285::AID-QUA2>3.0.CO;2-S.
[14] H. J. Monkhorst and J. D. Pack, “Special points for Brillouin-zone integrations,” Phys. Rev. B, vol. 13, no. 12, 1976, doi: 10.1103/PhysRevB.13.5188.
[15] G. Henkelman, B. P. Uberuaga and H. Jónsson, “Climbing image nudged elastic band method for finding saddle points and minimum energy paths,” J. Chem. Physics, vol. 113, no. 22, 2000, doi: 10.1063/1.1329672.
[16] Z. N. Ezhyeh et al., “Review on doping strategy in Li4Ti5O12 as an anode material for Lithium-ion batteries,” Ceramics International, 2022, doi: 10.1016/J.CERAMINT.2022.04.340.