Skip to main content

Advertisement

Log in

Synergic effect of nanostructuring and excess Mn3+ content in the electrochemical performance of Li4Ti5O12–LiNi0.5Mn1.5O4 Li-ion full-cells

  • Article
  • Published:
Journal of Materials Research Aims and scope Submit manuscript

Abstract

The design of high energy Li-ion batteries (LIBs) by coupling high voltage LiNi0.5Mn1.5O4 (LNMO) cathode and Li4Ti5O12 (LTO) anode ensures effective and safe energy-storage. LTO–LNMO full-cells (FCs) with difference in electrode grain sizes and presence of excess Mn3+ in cathode were studied using micron-sized commercial LTO, nanostructured LTO donuts (LTOd), P4332 LNMO nanopowders, and nanostructured Fd3m LNMO caterpillars (LNMOcplr). Among the studied FCs, LTOd–LNMOcplr was detected with a stable capacity of 69 mA h/g (1C rate), 99% coulombic efficiency, and 87% capacity retention under 200 cycles of continuous charge–discharge studies. The superior electrochemical performance observed in LTOd–LNMOcplr FC was due to the low charge transfer resistance, which is corroborated to the effect of grain sizes and the longer retention of Mn3+ in the electrodes. An effective and simple FC design incorporating both nanostructuring and in situ conductivity in electrode materials would aid in developing future high-performance LIBs.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5

Similar content being viewed by others

References

  1. M. Wakihara: Recent developments in lithium ion batteries. Mater. Sci. Eng., R 33, 109 (2001).

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  3. P.G. Bruce, B. Scrosati, and J-M. Tarascon: Nanomaterials for rechargeable lithium batteries. Angew. Chem., Int. Ed. 47, 2930 (2008).

    Article  CAS  Google Scholar 

  4. S.Y. Yin, L. Song, X.Y. Wang, M.F. Zhang, K.L. Zhang, and Y.X. Zhang: Synthesis of spinel Li4Ti5O12 anode material by a modified rheological phase reaction. Electrochim. Acta 54, 5629 (2009).

    Article  CAS  Google Scholar 

  5. N.M. Tikekar, J.J. Lannutti, R. Rao Revur, and S. Sengupta: High surface area lithium titanate electrode for Li-ion batteries. J. New Mater. Electrochem. Syst. 15, 265 (2012).

    Article  CAS  Google Scholar 

  6. Y. Li, G.L. Pan, J.W. Liu, and X.P. Gao: Preparation of Li4Ti5O12 nanorods as anode materials for lithium-ion batteries. J. Electrochem. Soc. 156, A495 (2009).

    Article  CAS  Google Scholar 

  7. W-J. Zhang: A review of the electrochemical performance of alloy anodes for lithium-ion batteries. J. Power Sources 196, 13 (2011).

    Article  CAS  Google Scholar 

  8. T. Ohzuku: Zero-strain insertion material of Li [Li1/3Ti5/3]O4 for rechargeable lithium cells. J. Electrochem. Soc. 142, 1431 (1995).

    Article  CAS  Google Scholar 

  9. Z. Choi, D. Kramer, and R. Monig: Correlation of stress and structural evolution in Li4Ti5O12-based electrodes for lithium ion batteries. J. Power Sources 240, 245 (2013).

    Article  CAS  Google Scholar 

  10. A. Zhang, Z. Zheng, F. Cheng, Z. Tao, and J. Chen: Preparation of Li4Ti5O12 submicrospheres and their application as anode materials of rechargeable lithium-ion batteries. Sci. China Chem. 54, 936 (2011).

    Article  CAS  Google Scholar 

  11. Y. Tang, F. Huang, W. Zhao, Z. Liu, and D. Wan: Synthesis of graphene supported Li4Ti5O12 nanosheets for high rate battery application. J. Mater. Chem. 22, 11257 (2012).

    Article  CAS  Google Scholar 

  12. J. Wang, X. Liu, and H. Yang: Synthesis and electrochemical properties of highly dispersed Li4Ti5O12 nanocrystalline for lithium secondary batteries. Trans. Nonferrous Met. Soc. China 22, 613 (2012).

    Article  Google Scholar 

  13. T-F. Yi, L-J. Jiang, J. Shu, C-B. Yue, R-S. Zhu, and H-B. Qiao: Recent development and application of Li4Ti5O12 as anode material of lithium ion battery. J. Phys. Chem. Solids 71, 1236 (2010).

    Article  CAS  Google Scholar 

  14. A. Guerfi, S. Sévigny, M. Lagacé, P. Hovington, K. Kinoshita, and K. Zaghib: Nanoparticle Li4Ti5O12 spinel as electrode for electrochemical generators. J. Power Sources 119–121, 88 (2003).

    Article  Google Scholar 

  15. K. Mizushima, P.C. Jones, P.J. Wiseman, and J.B. Goodenough: LixCoO2 (0 < x ≤ 1): A new cathode material for batteries of high energy density. Solid State Ionics 3–4, 171 (1981).

    Article  Google Scholar 

  16. J. Xiao, X. Chen, P.V. Sushko, M.L. Sushko, L. Kovarik, J. Feng, Z. Deng, J. Zheng, G.L. Graff, Z. Nie, D. Choi, J. Liu, J.G. Zhang, and M.S. Whittingham: High-performance LiNi0.5Mn1.5O4 Spinel controlled by Mn3+ concentration and site disorder. Adv. Mater. 24, 2109 (2012).

    Article  CAS  Google Scholar 

  17. J. Kim, S. Myung, C.S. Yoon, S.G. Kang, and Y. Sun: Comparative study of cathodes having two crystallographic structures: Fd3m and P4332. Chem. Mater. 10, 906 (2004).

    Article  CAS  Google Scholar 

  18. L. Wang, H. Li, X. Huang, and E. Baudrin: A comparative study of \(Fd\bar 3m\) and P4332 “LiNi0.5Mn1.5O4”. Solid State Ionics 193, 32 (2011).

    Article  CAS  Google Scholar 

  19. J. Yang, X. Han, X. Zhang, F. Cheng, and J. Chen: Spinel LiNi0.5Mn1.5O4 cathode for rechargeable lithium ion batteries: Nano vs micro, ordered phase (P4332) vs disordered phase \(Fd\bar 3m\). Nano Res. 6, 679 (2013).

    Article  CAS  Google Scholar 

  20. J. Song, D.W. Shin, Y. Lu, C.D. Amos, A. Manthiram, and J.B. Goodenough: Role of oxygen vacancies on the performance of Li[Ni0.5−xMn1.5+x]O4 (x = 0, 0.05, and 0.08) spinel cathodes for lithium-ion batteries. Chem. Mater. 24, 3101 (2012).

    Article  CAS  Google Scholar 

  21. J. Zheng, J. Xiao, X. Yu, L. Kovarik, M. Gu, F. Omenya, X. Chen, X.Q. Yang, J. Liu, G.L. Graff, M.S. Whittingham, and J.G. Zhang: Enhanced Li+-ion transport in LiNi0.5Mn1.5O4 through control of site disorder. Phys. Chem. Chem. Phys. 14, 13515 (2012).

    Article  CAS  Google Scholar 

  22. A.K. Haridas, C.S. Sharma, and T.N. Rao: Donut-shaped Li4Ti5O12 structures as a high-performance anode material for lithium ion batteries. Small 11, 290 (2015).

    Article  CAS  Google Scholar 

  23. A.K. Haridas, C.S. Sharma, and T.N. Rao: Caterpillar-like sub-micron LiNi0.5Mn1.5O4 structures with site disorder and excess Mn3+ as high-performance cathode material for lithium ion batteries. Electrochim. Acta 212, 500 (2016).

    Article  CAS  Google Scholar 

  24. M. Kunduraci and G.G. Amatucci: Synthesis and characterization of nanostructured 4.7 V LixMn1.5Ni0.5O4 spinels for high-power lithium-ion batteries. J. Electrochem. Soc. 153, A1345 (2006).

    Article  CAS  Google Scholar 

  25. G. Liu, Y. Li, B. Ma, and Y. Li: Study of the intrinsic electrochemical properties of spinel LiNi0.5Mn1.5O4. Electrochim. Acta 112, 557 (2013).

    Article  CAS  Google Scholar 

  26. N. Amdouni, K. Zaghib, F. Gendron, A. Mauger, and C.M. Julien: Structure and insertion properties of disordered and ordered LiNi0.5Mn1.5O4 spinels prepared by wet chemistry. Ionics 12, 117 (2006).

    Article  CAS  Google Scholar 

  27. H.F. Xiang, X. Zhang, Q.Y. Jin, C.P. Zhang, C.H. Chen, and X.W. Ge: Effect of capacity matchup in the LiNi0.5Mn1.5O4/Li4Ti5O12 cells. J. Power Sources 183, 355 (2008).

    Article  CAS  Google Scholar 

  28. J. Zheng, J. Xiao, Z. Nie, and J-G. Zhang: Lattice Mn3+ behaviours in Li4Ti5O12/LiNi0.5Mn1.5O4 full cells. J. Electrochem. Soc. 160, A1264 (2013).

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Authors acknowledge Nano Mission project provided by Department of Science and Technology (DST), India for the entire funding. TNR and AKH extend their sincere gratitude to Dr. B.V. Sarada of ARCI, Hyderabad for Micro Raman data.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Chandra S. Sharma or Tata N. Rao.

Supplementary Material

43578_2020_35010042_MOESM1_ESM.docx

Synergic effect of Nanostructuring and Excess Mn3+ Content in the Electrochemical Performance of Li4Ti5O12–LiNi0.5Mn1.5O4 Li-Ion Full-cells, approximately 496 KB

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Haridas, A.K., Jyothirmayi, A., Sharma, C.S. et al. Synergic effect of nanostructuring and excess Mn3+ content in the electrochemical performance of Li4Ti5O12–LiNi0.5Mn1.5O4 Li-ion full-cells. Journal of Materials Research 35, 42–50 (2020). https://doi.org/10.1557/jmr.2019.304

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1557/jmr.2019.304

Navigation