Skip to main content

Advertisement

SpringerLink
Log in

Sr–Y co-doped LiNi0.5Mn1.5O4 cathode material with modified crystal and improved electrochemical performance

  • Energy materials
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

LiNi0.5Mn1.5O4 (LNMO), as a promising cathode material for high energy density lithium-ion batteries, has been limited by its intrinsic side effects with electrolytes at high voltage resulting in serious Mn dissolution and capacity attenuation. To address this issue, a sol–gel method was used to prepare LiNi0.49Mn1.49−xSrxY0.02O4 (x = 0.02, 0.04, 0.06). In addition, the LNMO material co-doped with Sr and Y was also studied for its crystal structure, microscopic morphology, and electrochemical properties. Structural characterization has revealed that the doping of Sr2+ and Y3+ into the LNMO material results in a reduction in particle size, a decrease in the content of Mn3+, and an increased proportion of the (100) crystal plane of the LNMO material. These modifications contribute to an improvement in the electrochemical performance of the LNMO material. The LiNi0.49Mn1.45Sr0.04Y0.02O4 LNMO sample showed the optimal electrochemical performance, with a discharge capacity of 131.84 mAh g−1 after 100 cycles at 1 C, retaining 95.55% of its initial capacity, and achieving a specific capacity of 104.79 mAh g−1 at 5 C.

Graphical abstract

New Sr and Y co-doping strategy was designed and LiNi0.49Mn1.49−xSrxY0.02O4 (x = 0.02, 0.04, 0.06) sample was obtained via citric acid aided route to enhance the electrochemical property of LiNi0.5Mn1.5O4 cathode material for the first time.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10

Similar content being viewed by others

Data availability

The data that support the findings of this study are available on request from the corresponding authors.

References

  1. Wang C, Wang S, He Y, Tang L, Han C, Yang C et al (2015) Combining fast Li-Ion battery cycling with large volumetric energy density: grain boundary induced high electronic and ionic conductivity in Li4Ti5O12 spheres of densely packed nanocrystallites. Chem Mater 27(16):5647–5656. https://doi.org/10.1021/acs.chemmater.5b02027

    Article  CAS  Google Scholar 

  2. Zhou L, Zhao D, Lou XD (2012) LiNi0.5Mn1.5O4 hollow structures as high-performance cathodes for lithium-ion batteries. Angew Chem Int Ed 51(1):239–241. https://doi.org/10.1002/anie.201106998

    Article  CAS  Google Scholar 

  3. Qureshi ZA, Tariq HA, Shakoor RA, Kahraman R, Alqaradawi S (2022) Impact of coatings on the electrochemical performance of LiNi0.5Mn1.5O4 cathode materials: a focused review. Ceram Int 48(6):7374–7392. https://doi.org/10.1016/j.ceramint.2021.12.118

    Article  CAS  Google Scholar 

  4. Schmuch R, Wagner R, Horpel G, Placke T, Winter M (2018) Performance and cost of materials for lithium-based rechargeable automotive batteries. Nat Energy 3(4):267–278. https://doi.org/10.1038/s41560-018-0107-2

    Article  CAS  Google Scholar 

  5. Wu L, Huo H, Wang Q, Yin X, Guo S, Wang J et al (2022) Tuning the phase evolution pathway of LiNi0.5Mn1.5O4 synthesis from binary intermediates to ternary intermediates with thermal regulating agent. J Energy Chem 65:62–70. https://doi.org/10.1016/j.jechem.2021.05.031

    Article  CAS  Google Scholar 

  6. Lee JH, Kim KJ (2013) Superior electrochemical properties of porous Mn2O3-coated LiMn2O4 thin-film cathodes for Li-ion microbatteries. Electrochim Acta 102:196–201. https://doi.org/10.1016/j.electacta.2013.03.170

    Article  CAS  Google Scholar 

  7. Pieczonka N, Liu ZY, Lu P, Olson KL, Moote J, Powell BR et al (2013) Understanding transition-metal dissolution behavior in LiNi0.5Mn1.5O4 high-voltage spinel for lithium ion batteries. J Phys Chem C 117(31):15947–15957. https://doi.org/10.1021/jp405158m

    Article  CAS  Google Scholar 

  8. Wang Q, Peng DC, Chen YX, Xia XH, Liu HB, He YD et al (2018) A facile surfactant-assisted self-assembly of LiFePO4/graphene composites with improved rate performance for lithium ion batteries. J Electroanal Chem 818:68–75. https://doi.org/10.1016/j.jelechem.2018.04.030

    Article  CAS  Google Scholar 

  9. Zhang MH, Liu YZ, Xia YG, Qiu B, Wang J, Liu ZP (2014) Simplified co-precipitation synthesis of spinel LiNi0.5Mn1.5O4 with improved physical and electrochemical performance. J Alloy Compd 598:73–78. https://doi.org/10.1016/j.jallcom.2014.02.034

    Article  CAS  Google Scholar 

  10. Han Y, Jiang YS, Xia Y, Deng L, Que LF, Yu FD et al (2022) Suppressed phase separation in spinel LiNi0.5Mn1.5O4 cathode via interstitial sites modulation. Nano Energy 91:24–32. https://doi.org/10.1016/j.nanoen.2021.106636

    Article  CAS  Google Scholar 

  11. Liu GQ, Wen L, Wang X, Ma BY (2011) Effect of the impurity LixNi1-xO on the electrochemical properties of 5 V cathode material LiNi0.5Mn1.5O4. J Alloy Compd 509(38):9377–9381. https://doi.org/10.1016/j.jallcom.2011.07.045

    Article  CAS  Google Scholar 

  12. Potapenko AV, Kirillov SA (2017) Enhancing high-rate electrochemical properties of LiMn2O4 in a LiMn2O4/LiNi(0.5)Mn(1.5)O(4)core/shell composite. Electrochim Acta 258:9–16. https://doi.org/10.1016/j.electacta.2017.10.108

    Article  CAS  Google Scholar 

  13. Shang XH, Hu B, Nie PF, Shi W, Hussain T, Liu JY (2021) LiNi0.5Mn1.5O4-based hybrid capacitive deionization for highly selective adsorption of lithium from brine. Sep Purif Technol. https://doi.org/10.1016/j.seppur.2020.118009

    Article  Google Scholar 

  14. Feng SP, Kong X, Sun HY, Wang BS, Luo TB, Liu GY (2018) Effect of Zr doping on LiNi0.5Mn1.5O4 with ordered or disordered structures. J Alloy Compd 749:1009–1018. https://doi.org/10.1016/j.jallcom.2018.03.177

    Article  CAS  Google Scholar 

  15. Huang Y, Liu X, Yu RZ, Cao S, Pei Y, Luo ZG et al (2019) Tellurium surface doping to enhance the structural stability and electrochemical performance of layered Ni-rich cathodes. Acs Appl Mater Inter 11(43):40022–40033. https://doi.org/10.1021/acsami.9b13906

    Article  CAS  Google Scholar 

  16. Kim MC, Lee YW, Pham TK, Sohn JI, Park KW (2020) Chemical valence electron-engineered LiNi0.4Mn1.5MtO4 (M-t = Co and Fe) cathode materials with high-performance electrochemical properties. Appl Surf Sci. https://doi.org/10.1016/j.apsusc.2019.144514

    Article  Google Scholar 

  17. Li SY, Wei Y, Wang P, Feng YH, Liang WB, Ding H et al (2020) Synergism of Cu and Al co-doping on improvements of structural integrity and electrochemical performance for LiNi0.5Mn1.5O4. J Alloy Compd. https://doi.org/10.1016/j.jallcom.2019.153140

    Article  Google Scholar 

  18. Kocak T, Wu LY, Wang J, Savaci U, Turan S, Zhang XG (2021) The effect of vanadium doping on the cycling performance of LiNi0.5Mn1.5O4 spinel cathode for high voltage lithium-ion batteries. J Electroanal Chem. https://doi.org/10.1016/j.jelechem.2020.114926

    Article  Google Scholar 

  19. Wei AJ, Mu JP, He R, Bai X, Li XH, Wang YJ et al (2021) Li+ and Cl- co-doped LiNi0.5Mn1.5O4 cathode material with truncated octahedral shape and enhanced electrochemical performance for Li-ion batteries. Solid State Ion. https://doi.org/10.1016/j.ssi.2021.115753

    Article  Google Scholar 

  20. George G, Jackson SL, Luo CQ, Fang D, Luo D, Hu D et al (2018) Effect of doping on the performance of high-crystalline SrMnO3 perovskite nanofibers as a supercapacitor electrode. Ceram Int 44(17):21982–21992. https://doi.org/10.1016/j.ceramint.2018.08.313

    Article  CAS  Google Scholar 

  21. Ji X, Dai X, Wu F, Mai Y, Chen H, Gu Y (2021) In situ Sr2+-doped spinel LiNi0.5Mn1.5O4 cathode material for Li-ion batteries with high electrochemical performance and its impact on morphology. Ceram Int 47(22):32043–32052. https://doi.org/10.1016/j.ceramint.2021.08.093

    Article  CAS  Google Scholar 

  22. Zong B, Deng ZY, Yan SH, Lang YQ, Gong JJ, Guo JL et al (2020) Effects of Si doping on structural and electrochemical performance of LiNi0.5Mn1.5O4 cathode materials for lithium-ion batteries. Powder Technol 364:725–737. https://doi.org/10.1016/j.powtec.2020.02.033

    Article  CAS  Google Scholar 

  23. Wu W, Guo JL, Qin X, Bi CB, Wang JF, Wang L et al (2017) Enhanced electrochemical performances of LiNi0.5Mn1.5O4 spinel in half -cell and full -cell via yttrium doping. J Alloy Compd 721:721–730. https://doi.org/10.1016/j.jallcom.2017.06.060

    Article  CAS  Google Scholar 

  24. Liu H, Kloepsch R, Wang J, Winter M, Li J (2015) Truncated octahedral LiNi0.5Mn1.5O4 cathode material for ultralong-life lithium-ion battery: positive (100) surfaces in high-voltage spinel system. J Power Sources 300:430–437. https://doi.org/10.1016/j.jpowsour.2015.09.066

    Article  CAS  Google Scholar 

  25. Chen T, Lin F, Wu H, Zhou D, Song J, Guo J (2023) Zn-Y co-doped LiNi0.5Mn1.5O4 cathode materials with high electrochemical performance. J Alloy Compd 941:168825. https://doi.org/10.1016/j.jallcom.2023.168825

    Article  CAS  Google Scholar 

  26. Lin F, Wu H, Chen T, Zhou D, Yan W, Guo J (2022) The action of Y-F co-doping in LiNi0.5Mn1.5O4 positive electrode materials. Powder Technol 409:117812. https://doi.org/10.1016/j.powtec.2022.117812

    Article  CAS  Google Scholar 

  27. Bai X, Wei AJ, He R, Li W, Li XH, Zhang LH et al (2020) The structural and electrochemical performance of Mg-doped LiNi0.85Co0.10Al0.05O2 prepared by a solid state method. J Electroanal Chem. https://doi.org/10.1016/j.jelechem.2019.113771

    Article  Google Scholar 

  28. Zhu RN, Zhang SJ, Guo QX, Zhou Y, Li JT, Wang PF et al (2020) More than just a protection layer: inducing chemical interaction between Li3BO3 and LiNi0.5Mn1.5O4 to achieve stable high-rate cycling cathode materials. Electrochim Acta. https://doi.org/10.1016/j.electacta.2020.136074

    Article  Google Scholar 

  29. Baggetto L, Dudney NJ, Veith GM (2013) Surface chemistry of metal oxide coated lithium manganese nickel oxide thin film cathodes studied by XPS. Electrochim Acta 90:135–147. https://doi.org/10.1016/j.electacta.2012.11.120

    Article  CAS  Google Scholar 

  30. Hosono E, Kudo T, Honma I, Matsuda H, Zhou HS (2009) Synthesis of single crystalline spinel LiMn2O4 nanowires for a lithium ion battery with high power density. Nano Lett 9(3):1045–1051. https://doi.org/10.1021/nl803394v

    Article  CAS  Google Scholar 

  31. Wang SN, Hua WB, Zhou S, He XF, Liu LJ (2020) In situ synchrotron radiation diffraction study of the Li+ de/intercalation behavior in spinel LiNi0.5Mn1.5O4-delta. Chem Eng J. https://doi.org/10.1016/j.cej.2020.125998

    Article  Google Scholar 

  32. Yi TF, Li YM, Li XY, Pan JJ, Zhang Q, Zhu YR (2017) Enhanced electrochemical property of FePO4-coated LiNi0.5Mn1.5O4 as cathode materials for Li-ion battery. Sci Bull 62(14):1004–1010. https://doi.org/10.1016/j.scib.2017.07.003

    Article  CAS  Google Scholar 

  33. Yan SP, Sun XL, Zhang Y, Fu SX, Lang YQ, Wang L et al (2022) From coating to doping: effect of post-annealing temperature on the alumina coating of LiNi0.5Mn1.5O4 cathode material. J Solid State Chem. https://doi.org/10.1016/j.jssc.2021.122765

    Article  Google Scholar 

  34. Wei AJ, Mu JP, He R, Bai X, Liu Z, Zhang LH et al (2021) Enhancing electrochemical performance and structural stability of LiNi0.5Mn1.5O4 cathode material for rechargeable lithium-ion batteries by boron doping. Ceram Int 47(1):226–237. https://doi.org/10.1016/j.ceramint.2020.08.125

    Article  CAS  Google Scholar 

  35. Mo MY, Hui KS, Hong XT, Guo JS, Ye CC, Li AJ et al (2014) Improved cycling and rate performance of Sm-doped LiNi0.5Mn1.5O4 cathode materials for 5 V lithium ion batteries. Appl Surf Sci 290:412–418. https://doi.org/10.1016/j.apsusc.2013.11.094

    Article  CAS  Google Scholar 

  36. Liu H, Wang J, Zhang X, Zhou D, Qi X, Qiu B et al (2016) Morphological evolution of high-voltage spinel LiNi0.5Mn1.5O4 cathode materials for lithium-ion batteries: the critical effects of surface orientations and particle size. Acs Appl Mater Inter 8(7):4661–4675. https://doi.org/10.1021/acsami.5b11389

    Article  CAS  Google Scholar 

  37. Yi TF, Chen B, Zhu YR, Li XY, Zhu RS (2014) Enhanced rate performance of molybdenum-doped spinet LiNi0.5Mn1.5O4 cathode materials for lithium ion battery. J Power Sources 247:778–785. https://doi.org/10.1016/j.jpowsour.2013.09.031

    Article  CAS  Google Scholar 

  38. Gao C, Liu HP, Bi SF, Fan SS, Meng XH, Li QY et al (2020) Insight into the effect of graphene coating on cycling stability of LiNi0.5Mn1.5O4: integration of structure-stability and surface-stability. J Materiomics 6(4):712–722. https://doi.org/10.1016/j.jmat.2020.05.010

    Article  Google Scholar 

  39. Mu J, Zhang L, He R, Li X, Bai X, Tian L et al (2021) Enhancing the electrochemical performance of LiNi0.5Mn1.5O4 cathode material by a conductive LaCoO3 coating. J Alloy Compd 865:158629. https://doi.org/10.1016/j.jallcom.2021.158629

    Article  CAS  Google Scholar 

  40. Li HY, Luo Y, Xie JY, Zhang QS, Yan LQ (2015) Effect of lithium and fluorine doping on the electrochemical and thermal stability of LiNi0.5Mn1.5O4 spinel cathode material. J Alloy Compd 639:346-351. https://doi.org/10.1016/j.jallcom.2015.03.114

    Article  CAS  Google Scholar 

  41. Xiong L, Liu W, Wu Y, He Z (2015) Synthesis and characterization of LiNi0.49Mn1.49Y0.02O4@Ag by electroless plating technique. Appl Surf Sci 328:531-535. https://doi.org/10.1016/j.apsusc.2014.12.102

    Article  CAS  Google Scholar 

  42. Xu Y, Zhao S, Deng Y, Deng H, Nan C (2016) Improved electrochemical performance of 5 V spinel LiNi0.5Mn1.5O4 microspheres by F-doping and Li4SiO4 coating. J Materiomics 2(3):265-272. https://doi.org/10.1016/j.jmat.2016.04.005

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Natural Science Foundation of China (52063005), Science and Technology Support Project of Guizhou Province (2021488), Guizhou Province High-level Innovative Talents Training Project (2016/5667). Science and Technology Support Project of Guizhou Province, 2023356, Jianbing Guo.

Author information

Authors and Affiliations

  1. Department of Polymer Materials and Engineering, College of Materials and Metallurgy, Guizhou University, Guiyang, 550025, China

    Xingfu Zi & Jianbing Guo

  2. Guizhou Qiancai S&T Development Co., Ltd., Guiyang, 550003, China

    Xin Huang & Jiling Song

  3. National Engineering Research Center for Compounding and Modification of Polymer Materials, Guiyang, 550014, China

    Jiling Song, Hongming Wu & Jianbing Guo

Authors
  1. Xingfu Zi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xin Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jiling Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hongming Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jianbing Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

XZ contributed to experimental ideas and scheme design, writing-original draft preparation, data curation, writing-reviewing and editing. XH contributed to instructional support. JS contributed to writing-reviewing and editing. HW contributed to instructional support, writing-reviewing. JG contributed to funding acquisition, provision of study materials, reagents and materials.

Corresponding authors

Correspondence to Jiling Song or Jianbing Guo.

Ethics declarations

Conflict of interest

The authors have claimed that the work reported in this article will not generate conflicts of interest or economic disputes among them.

Ethical approval

Not applicable.

Additional information

Handling Editor: Kevin Jones.

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zi, X., Huang, X., Song, J. et al. Sr–Y co-doped LiNi0.5Mn1.5O4 cathode material with modified crystal and improved electrochemical performance. J Mater Sci 58, 12271–12287 (2023). https://doi.org/10.1007/s10853-023-08793-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-023-08793-w

Search

Navigation