Advertisement

Ionics

pp 1–7 | Cite as

DFT study of Li2NiTiO4 and vanadium-doped Li2NiTiO4

  • Shamik ChakrabartiEmail author
  • K. Biswas
Original Paper
  • 16 Downloads

Abstract

Density functional theory study of Li2NiTiO4 and vanadium-doped Li2NiTiO4 are performed for understanding their structural and electrochemical phenomena, viz., structural geometry like lattice parameters, change in lattice volume with Li+ extraction, Li+ de-intercalation voltage, electrochemical capacity etc. Li2NiTiO4 has cubic symmetry with space group Fm3m (space group number 225). De-intercalated structure of LiNiTiO4 is obtained by removing one Li atom from Li2NiTiO4 unit cell while shifting another Li atom from octahedral site 4b to tetrahedral lattice site 8c. Due to Li+ extraction, the change in unit cell volume is ~ 5.9%. Li+ de-intercalation voltage is calculated by subtracting total energy of the unit cell of LiNiTiO4 and bcc Li from Li2NiTiO4. The voltage comes out to be 4.84 V which is nearly at the threshold for electrochemical stability of used electrolytes. The redox couples in this case are Ni+2/Ni2 + δ and O−2/O−2+γ. The presence of redox couple O−2/O−2+γ leads to the probability of evolution of oxygen during charging. However, partial (50% in this case) vanadium doping at Ti site reduces the redox voltage to 4.64 V considering the de-intercalation reaction forming LiNiTi0.5V0.5O4 from Li2NiTi0.5V0.5O4, by activating the redox couple V+3/V+4 in Li2NiTi0.5V0.5O4. This also reduces the possibility of evolution of oxygen during de-intercalation reaction by shifting the main redox couple from O−2/O−2+γ to V+3/V+4, which leads to greater structural stability of electrode materials during charge-discharge cycles.

Keywords

Li-ion batteries Density functional theory Electronic structure De-intercalation voltage 

Notes

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. 1.
    Shukla AK, Kumar TP (2008) Materials for next generation lithium batteries. Curr Sci 94:314–331Google Scholar
  2. 2.
    Chakrabarti S, Thakur AK, Biswas K (2016) Density functional theory study of LiFeTiO4. J Power Sources 313:81–90CrossRefGoogle Scholar
  3. 3.
    Chakrabarti S, Thakur AK, Biswas K (2013) DFT analysis of lithium de-intercalation in Li2FeVO4. Ionics 19:1515–1526CrossRefGoogle Scholar
  4. 4.
    Zin EM, Zin B, Jeon Y-S, Park K-H, Gu H-B (2009) Electrochemical properties of LiMnO2 for lithium polymer battery. J Power Sources 189:620–623CrossRefGoogle Scholar
  5. 5.
    Sheu SP, Shih IC, Yao CY, Chen JM, Hurng WM (1997) Studies of LiNiO2 in lithium-ion batteries. J Power Sources 68:558–560CrossRefGoogle Scholar
  6. 6.
    Kalyani P, Kalaiselvi N (2005) Various aspects of LiNiO2 chemistry: A review. Sci Technol Adv Mater 6:689–703CrossRefGoogle Scholar
  7. 7.
    Cheruku R, Vijayan L, Govindaraj G (2013) Structural and electrical conductivity studies of nanocrystalline Li2NiTiO4 material. Indian J Pure and Appl Physics 51:343–345Google Scholar
  8. 8.
    Trócoli R, Cruz-Yusta M, Morales J, Santos-Peña J (2013) On the limited electroactivity of Li2NiTiO4 nanoparticles in lithium batteries. Electrochim Acta 100:93–100CrossRefGoogle Scholar
  9. 9.
    Prabaharana SRS, Michael MS, Ikuta H, Uchimotob Y, Wakihara M (2004) Li2NiTiO4 – a new positive electrode for lithium batteries: soft-chemistry synthesis and electrochemical characterization. Solid State Ionics 172:39–45CrossRefGoogle Scholar
  10. 10.
    Wang Y, Wangand Y, Wang F (2014) Facile molten salts synthesis of Li2NiTiO4 cathode. Mater Li-ion Batter Nano Scale Res Lett 9:197–201Google Scholar
  11. 11.
    Kawano Y, Kitajou A, Okada S (2013) Synthesis and cathode properties of a cubic rock-salt type Si-doped Li2NiTiO4 for lithium-ion batteries. J Power Sour 242:768–774CrossRefGoogle Scholar
  12. 12.
    Küzma M, Dominko R, Meden A, Makovec D, Bele M, Jamnik J, Gaberscek M (2009) Electrochemical activity of Li2FeTiO4 and Li2MnTiO4 as potential active materials for Li ion batteries: a comparison with Li2NiTiO4. J Power Sour 189:81–88CrossRefGoogle Scholar
  13. 13.
    Wu J, Wang H, Quan J, Ma Z, Li D (2015) Enhanced electrochemical performance of Li2NiTiO4 with micro-structural rearrangement via urea treatment. RSC Adv 5:2844–2850CrossRefGoogle Scholar
  14. 14.
    Hamaguchi M, Momida H, Oguchi T (2018) First-principles study on cathode properties of Li2MTiO4 (M =V, Cr, Mn, Fe, Co, and Ni) with oxygen deficiency for Li-ion batteries. J Phys Soc Jpn 87:044805-1–044805-8CrossRefGoogle Scholar
  15. 15.
    Kresse G, Marsman M and Furthmuller J, Computational Materials Physics, Faculty of Physics, Universitat Wien, Sensengasse 8/12, A-1090 Wien, Austria, https://www.vasp.at/
  16. 16.
    Blaha P, Schwarz K, Madsen GKH, Kvasnicka D and Luitz J, WIEN2k, An Augmented Plane Wave + Local Orbitals Programme for Calculating Crystal Properties (Karlheinz Schwarz, Techn. Universitat Wien, Austria), 2001.ISBN 3-9501031-1-2,Google Scholar
  17. 17.
    Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77(18):3865–3868CrossRefGoogle Scholar
  18. 18.
    Chakrabarti S, Biswas K (2017) DFT study of Mg2TiO4 and Ni doped Mg1.5Ni0.5TiO4 as electrode material for Mg ion battery application. J Mater Sci 52:10972–10980CrossRefGoogle Scholar
  19. 19.
    Aydinol MK, Kohan AF, Ceder G (1997) Ab initio calculation of the intercalation voltage of lithium-transition-metal oxide electrodes for rechargeable batteries. J Power Sour 68:664–668CrossRefGoogle Scholar
  20. 20.
    Chakrabarti S, Thakur AK, Biswas K (2017) Effect of Ti modification on Structural, Electronic and Electrochemical properties of Li2FeSiO4—A DFT study using FPLAPW approach. Electrochim Acta 236:288–296CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Condensed Matter Physics and Materials ScienceSN Bose National Centre for Basic SciencesKolkataIndia
  2. 2.Department of Metallurgical and Materials EngineeringIIT KharagpurKharagpurIndia

Personalised recommendations