Modeling of the Electronic Properties of M-Doped Supercells (М = Zr, Nb) with a Monoclinic Structure For Lithium-Ion Batteries

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Дәйексөз келтіру

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Рұқсат жабық Тек жазылушылар үшін

Аннотация

The T–x phase diagram of the quasi-binary system Li2O–TiO2 was refined and the isothermal cross section of the ternary Li–Ti–O system at 298 K was constructed. The equilibrium phase regions of Li–Ti–O in the solid state are determined with the participation of boundary binary oxides and four intermediate ternary compounds , ,  and . Using the density functional theory (DFT LSDA) method, the formation energies  of the indicated ternary compounds of the Li2O–TiO2 system were calculated and the dependence of  on the composition was plotted.

Ab initio modeling of supercells based on M-doped  anode material based on the  (LTO) compound with a monoclinic structure () was carried out. It has been shown that partial substitution of cations and oxygen in the m-LTO–M structure increases the efficiency of a lithium-ion battery (LIB) both by stabilizing the structure and by increasing the diffusion rate of . Due to the contribution of d-orbitals (Zr4+-4d, Nb3+-4d orbitals) to the exchange energy, partial polarization of electronic states occurs and the electronic conductivity of m-LTO–M increases. The formation of oxygen vacancies in the m-LTO–M crystal lattice, as in binary oxides, can create donor levels and improve the transport of and electrons.

M-doping of the m-LTO structure by replacing cations, in particular lithium, with Zr or Nb atoms noticeably reduces the band gap (Eg) of m-LTO–M supercells. In this case, in the m-LTO–M band structure, the Fermi level shifts to the conduction band and the band gap narrows. Decreasing the Eg value increases the electronic and lithium-ion conductivity of m-LTO–M supercells.

Авторлар туралы

M. Asadov

Nagiyev Institute of Catalysis and Inorganic Chemistry, Ministry of Science and Education of Azerbaijan; Scientific Research Institute of Geotechnological Problems of Oil, Gas and Chemistry

Хат алмасуға жауапты Автор.
Email: mirasadov@gmail.com
Әзірбайжан, Baku; Baku

S. Mammadova

Institute of Physics, Ministry of Science and Education of Azerbaijan; Khazar University

Email: mirasadov@gmail.com
Әзірбайжан, Baku; Baku

S. Mustafaeva

Institute of Physics, Ministry of Science and Education of Azerbaijan

Email: mirasadov@gmail.com
Әзірбайжан, Baku

S. Huseynova

Institute of Physics, Ministry of Science and Education of Azerbaijan; Khazar University

Email: mirasadov@gmail.com
Әзірбайжан, Baku; Baku

V. Lukichev

Valiev Physics and Technology Institute, Russian Academy of Sciences

Email: lukichev@ftian.ru
Ресей, Moscow

Әдебиет тізімі

  1. Reddy M.V., Subba Rao G.V., Chowdari B.V.R. Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries // Chemical Reviews 2013. V. 113. No. 7. P. 5364 –5457. https://doi.org/10.1021/cr3001884
  2. Tanaka S., Kitta M., Tamura T., Maeda Y., Akita T., Kohyama M. Atomic and electronic structures of Li4Ti5O12/Li7Ti5O12 (001) interfaces by first-principles calculations // J Mater Sci. 2014. https://doi.org/10.1007/s10853-014-8102-x
  3. Ikezawa A., Fukunishi. G, Okajima T., Kitamura F., Suzuki K., Hirayama M., Kanno R., Arai H. Performance of Li4Ti5O12-based Reference Electrode for the Electrochemical Analysis of Allsolid-state Lithium-ion Batteries // Electrochemistry Communications. 2020. V. 116. Р. 106743. https://doi.org/10.1016/j.elecom.2020.106743
  4. Ziebarth B., Klinsmann M., Eckl T., Elsässer C. Lithium diffusion in the spinel phase Li4Ti5O12 and in the rocksalt phase Li7Ti5O12 of lithium titanate from first principles // Physical Review B. 2014. V. 89. No. 17. P. 174301–7. https://doi.org/10.1103/physrevb.89.174301
  5. Xu G., Han P., Dong S., Liu H., Cui G., Chen L. Li4Ti5O12-based energy conversion and storage systems: status and prospects // Coordination Chemistry Reviews. 2017. S0010854517301121. P. 1–158. https://doi.org/10.1016/j.ccr.2017.05.0066.
  6. Zhang H., Yang Y., Xu H., Wang L., LX., He X. Li4Ti5O12 spinel anode: Fundamentals and advances in rechargeable batteries // InfoMat. 2022. 4: e12228. P. 1–29. https://doi.org/10.1002/inf2.12228
  7. Asadov M.M., Mammadova S.O., Huseynova S.S., Mustafaeva S.N., Lukichev V.F. Simulation of the Adsorption and Diffusion of Lithium Atoms on Defective Graphene for a Li-Ion Battery // Russian Microelectronics. 2023. V. 52. No. 3. P. 167–185. https://doi.org/10.1134/S1063739723700336
  8. Zhao B., Ran R., Liu M., Shao Z. A comprehensive review of Li4Ti5O12 based electrodes for lithium-ion batteries: The latest advancements and future perspectives // Materials Science and Engineering R. 2015. V. 98. P. 1–71. https://doi.org/10.1016/j.mser.2015.10.001
  9. Asadov M.M., Mammadova S.O., Guseinova S.S., Mustafaeva S.N., Lukichev V.F. Ab initio calculation of the band structure and properties of modifications of the Ti3Sb compound doped with lithium // Physics of the Solid State. 2022. V. 64. No. 11. P. 1594–1609. https://doi.org/10.21883/PSS.2022.11.54179.395
  10. Asadov M.M., Mammadova S.O., Guseinova S.S., Mustafaeva S.N., Lukichev V.F. Modeling of Gold Adsorption by the Surface of Defect Graphene // Russian Microelectronics. 2022. V. 51. No. 6. P. 413–425. https://doi.org/10.1134/S1063739722700159
  11. Asadov M.M., Mammadova S.O., Guseinova S.S., Mustafaeva S.N., Lukichev V.F. Modeling structural and energy characteristics of atoms in a GaS2D-crystal with point defects // Physics of the Solid State. 2022. V. 64. No. 1. P. 44–57. https://doi.org/10.21883/PSS.2022.01.52487.182
  12. Kleykamp H. Phase equilibria in the Li—Ti—O system and physical properties of Li2TiO3 // Fusion Engineering and Design. 2002. V. 61–62. P. 361–366. https://doi.org/10.1016/s0920-3796(02)00120-5
  13. Okamoto H. Li-O (Lithium-Oxygen) // Journal of Phase Equilibria and Diffusion. 2013. V. 34. No. 2. P. 169. https://doi.org/ 10.1007/s11669-012-0182-1
  14. Okamoto H. O-Ti (Oxygen-Titanium) // Journal of Phase Equilibria and Diffusion. 2011. V. 32. No. 5. P. 473–474. https://doi.org/10.1007/s11669-011-9935-5
  15. Bale C.W. The Li-Ti (Lithium-Titanium system). Bulletin of Alloy Phase Diagrams. 1989. V. 10. No. 2. P. 135–138. https://doi.org/10.1007/bf02881424
  16. Asadov M.M., Kuli-zade E.S. Phase equilibria, thermodynamic analysis and electrical properties of the Li2O—Y2O3—B2O3 system // Journal of Alloys and Compounds. JALCOM (IF 4.650) Pub Date: 2020–05–23. https://doi.org/10.1016/j.jallcom.2020.155632
  17. https://next-gen.materialsproject.org/materials/mp-685194. mp-685194: Li4Ti5O12 (Monoclinic, C2/c, 15).
  18. Li X., Qu M., Yu Z. Structural and electrochemical performances of Li4Ti5–xZrxO12 as anode material for lithium-ion batteries // Journal of Alloys and Compounds. 2009. V. 487. No. 1–2. P. L12—L17. https://doi.org/110.1016/j.jallcom.2009.07.176
  19. Kim S.-K., Kwon E.-S., Kim T.-H., Moon J., Kim J. Effects of atmospheric Ti (III) reduction on Nb2O5-doped Li4Ti5O12 anode materials for lithium ion batteries. Ceramics International. 2014. V. 40. No. 6. P. 8869–8874. https://doi.org/10.1016/j.ceramint.2013.12.132
  20. Wang L., Zhang Y. M., Guo H.Y., Li J., Stach E.A., Tong X., Takeuchi E.S., Takeuchi K.J., Liu P., Marschilok A.C., Wong S.S. Structural and Electrochemical Characteristics of Ca-Doped “Flowerlike” Li4Ti5O12 Motifs as High-Rate Anode Materials for Lithium-Ion Batteries // Chem Mater. 2018. V. 30. No. 3. P. 671–684.21.
  21. Tsai P., Hsu W-D., Lin S. Atomistic Structure and Ab Initio Electrochemical Properties of Defect Spinel for Li Ion Batteries // Journal of the Electrochemical Society. 2014. V. 161. No. 3. A439—A444. https://doi.org/10.1149/2.095403jes
  22. Ouyang C.Y., Zhong Z.Y., Lei M.S. Ab initio studies of structural and electronic properties of spinel // Electrochemistry Communication. 2007. V. 9. No 5. P. 1107–1112. https://doi.org/10.1016/j.elecom.2007.01.013
  23. Ding Z., Zhao L., Suo L., Jiao Y., Meng S., Hu Y-S., Wang Z., Chen L. Towards understanding the effects of carbon and nitrogen-doped carbon coating on the electrochemical performance of in lithium ion batteries: a combined experimental and theoretical study // Physical Chemistry Chemical Physics. 2011. V. 13. No. 33. P. 15127–15133. https://doi.org/10.1039/C1CP21513B
  24. Nguyen T.D.H., Pham H.D., Lin S.-Y., Lin M.-F. Featured properties of Li+-based battery anode: // RSC Advances. 2020. V. 10. No. 24. P. 14071–14079. https://doi.org/10.1039/D0RA00818D
  25. https://next-gen.materialsproject.org/materials/mp-772925: (Triclinic, P-1, 2) (materialsproject.org)
  26. Yeh J.-J., Lindau I. Atomic subshell photoionization cross sections and asymmetry parameters: 1≤Z≤103. 1985. V. 32. No. 1. P. 1–155. https://doi.org/10.1016/0092-640x(85)90016-627.
  27. Yeh J.-J. Atomic Calculation of Photoionization Crosssection and Asymmetry Parameters. Gordon and Breach. New Jersey, 1993.

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Әрекет
1. JATS XML
Жүктеу
2. Fig. 1. Crystal structure of Li4Ti5O12 (LTO): a - cubic spinel modification c-LTO; b - monoclinic modification m-LTO; c - triclinic modification t-LTO

Жүктеу (547KB)
Метадеректер
3. Fig. 2. Our refined phase diagram (a) of the Li2O-TiO2 system: 1 - Li2O + Li4TiO4; 2 - Li2O + L (liquid); 3 - L + Li4TiO4; 4 - Li4TiO4 + β-Li2TiO3 (ss), where - solid solutions; 5 - Li4TiO4 + γ-Li2TiO3 (ss); 6 - L + γ-Li2TiO3 (ss); 7 - γ-Li2TiO3 (ss); 8 - γ-Li2TiO3 (ss) + β - Li2TiO3; 9 - β-Li2TiO3 (ss); 10 - β-Li2TiO3 (ss) + Li4Ti5O12 (LTO); 11 - γ-Li2TiO3 (ss) + (LTO); 12 - γ-Li2TiO3 (ss) + Li2Ti3O7; 13 - Li2Ti3O7; 14 - β-Li2Ti3O7 (ss) + LTO; 15 - β-Li2Ti3O7 (ss) + TiO2; 16 - γ-Li2Ti3O7 (ss) +TiO2; 17 - L + TiO2; 18 - γ-Li2Ti3O7 (ss) + L; 19 - γ-Li2TiO3 (ss) + L; preliminary isothermal cross section (b) of the Li-Ti-O system at 298 K constructed by us; concentration dependence of the energy of formation of ternary compounds (c) in the Li2O-TiO2 system. The calculated values for the phases Li4TiO4, Li2TiO3, Li4Ti5O12 lie on the convex hull and are thermodynamically stable

Жүктеу (387KB)
Метадеректер
4. Fig. 3. Atomic structure with monoclinic structure m-LTO-M: a - m-LTO supercell; b - m-LTO-Zr supercell; c - m-LTO-Nb supercell; d - convection supercell m-LT-Nb

Жүктеу (615KB)
Метадеректер
5. Fig. 4. Zone structure of the m-LTO supercell (a); DOS of the m-LTO supercell (b). The Fermi energy is set equal to 0 eV

Жүктеу (370KB)
Метадеректер
6. Fig. 5. Li4Ti5O12 unit cell with cubic structure (a), where green tetrahedrons and green octahedrons are Li ions at position 8a, blue octahedrons are Li and Ti ions at position 16d, and red spheres are oxygen ions at position 32e [21]; atomic projection of the density of states of the Ti atom in c-LTO (b) calculated using a 1 × 1 × 3 DFT GGA supercell [22]; five d-orbitals of the atom (c) having different three-dimensional orientations. The orbitals are arranged in the diagram as their energy increases; diagram of Ti-3d(t2g) orbitals of the titanium atom in LTO (d). The orbitals are arranged in the diagram as their energy increases

Жүктеу (674KB)
Метадеректер
7. Fig. 6. Zone structures of 2 × 2 × 2 doped m-LTO-Zr (Nb) supercells with monoclinic structure calculated by the DFT LSDA method: a - m-LTO-Zr supercell; b - m-LTO-Nb supercell. The Fermi energy is set equal to 0 eV on the energy scale

Жүктеу (383KB)
Метадеректер
8. Fig. 7. Total and partial densities of electronic states (DOS and PDOS) of 2 × 2 × 2 supercells based on m-LTO with monoclinic structure doped with Zr (or Nb): a - DOS of m-LTO supercell doped with Zr; b - PDOS of m-LTO supercell doped with Zr (Zr - PDOS); c - DOS of m-LTO supercell doped with Nb; d - PDOS of m-LTO supercell doped with Nb (Nb - PDOS). The Fermi energy is equal to 0 eV on the energy scale

Жүктеу (545KB)
Метадеректер

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