Delicate lithium-manganese spinel LiMn2O4 of quasi-spherical morphology, obtained by hydrolysis of complex compounds, as cathode material for high-power current sources

Sviatoslav A. Kirillov
Joint Department of Electrochemical Energy Systems of the National Academy of Sciences of Ukraine, Kyiv, Ukraine

Anna V. Potapenko
Joint Department of Electrochemical Energy Systems of the National Academy of Sciences of Ukraine, Kyiv, Ukraine

Tetiana V. Lisnycha
Joint Department of Electrochemical Energy Systems of the National Academy of Sciences of Ukraine, Kyiv, Ukraine

Pagination: 108-118

DOI: https://doi.org/10.15407/akademperiodyka.444.108


Precipitation of hydroxides and carbonates from solutions containing complex compounds is a valuable industrial process enabling one to synthesize electrode materials with high density particles of microspherical morphology and high tap density. As a complex formation agent, ammonia is almost exclusively used in this process. Aiming at the search of other complex formation agents and the detailed studies of complex formation at precipitation, we have first investigated the hydrolysis of solutions containing citric acid. Equilibria in solutions containing citrate complexes of manganese and carbonates are computed. It is found that in Mn(NO3)2хC6H8O7∙H2O – уNa2CO3 systems, a neutral Mn(HCitr) complex dominates up to pH=9.5 and precipitation of MnCO3 from carbonate containing solutions begins at рН~6.5. Experiments show that MnCO3 precipitates from these systems in the form of openwork quasi-spherical aggregates formed by nanosized crystals. The synthesis of LiMn2O4 from this precursor does not influence the morphology of the material, and the resulting product consists of aggregates of less than 4 mkm and nanocrystals of ~90 nm. Electrochemical tests evidence that for the best samples, the specific capacity of 103 mAh/g can be achieved at 1 C current. At 20 C current, they deliver ~25 mAh/g capacity. After high-rate tests, in control cycles with 1 C current, the samples demonstrate high capacity retention, returning up to 98% of their initial capacity. This signifies their good prospects for using in high-rate batteries.


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REFERENCES

  1. Kirillov S.A. Electrode Materials and Electrolytes for High-Rate Electrochemical Energy Systems: A Review. Theor. Exp. Chem. 2015. 55(2): 73–95. DOI: https://doi.org/10.1007/s11237-019-09598-2
  2. Dong H., Koenig G.M. A review on synthesis and engineering of crystal precursors produced via coprecipitation for multicomponent lithium-ion battery cathode materials. Cryst. Eng. Comm. 2020. 22(9): 1514–1530. DOI: https://doi.org/10.1039/C9CE00679F
  3. van Bommel A., Dahn J.R. Analysis of the growth mechanism of coprecipitated spherical and dense nickel, manganese, and cobalt-containing hydroxides in the presence of aqueous ammonia. Chem. Mater. 2009. 21(8): 1500–1503. DOI: https://doi.org/10.1021/cm803144d
  4. Zhu Z., Zhang D., Yan H., Li W., Qilu. Precise preparation of high performance spherical hierarchical LiNi0.5Mn1.5O4 for 5 V lithium ion secondary batteries. J. Mater. Chem. A. 2013. 1(18): 5492–5496. DOI: https://doi.org/10.1039/C3TA10980A
  5. Robinson J.P., Koenig G.M. Tuning solution chemistry for morphology control of lithium-ion battery precursor particles. Powder Technol. 2015. 284: 225–230. DOI: https://doi.org/10.1016/j.powtec.2015.06.070
  6. Potapenko A.V., Kirillov S.A. Lithium manganese spinel materials for high-rate electrochemical applications. J. Energy Chem. 2014. 23(5): 543–558. DOI: https://doi.org/10.1016/S2095-4956(14)60184-4
  7. Smith R.M., Martell A.E. Critical Stability Constants. Vol. 4. Inorganic Complexes. New York and London: Plenum Press, 1976. DOI: https://doi.org/10.1007/978-1-4757-5506-0
  8. Müller B. ChemEQL (V 3.2). Manual. Eawag: Swiss Federal Institute of Aquatic Science and Technology. Kastanienbaum, Switzerland, 2015.
  9. Morel F.M.M. Principles of Aquatic Chemistry. Somerset: Wiley, 1983. DOI: https://doi.org/10.4319/lo.1985.30.2.0450
  10. He X.M., Li J.J., Cai Y., Wang Y., Ying J., Jiang C., Wan C. Preparation of spherical spinel LiMn2O4 cathode material for lithium ion batteries. J. Solid State Electrochem. 2005. 9(6): 438–444. DOI: https://doi.org/10.1007/s10008-004-0593-y
  11. Potapenko A.V. Chernukhin S.I., Kirillov S.A. A new method of pretreatment of lithium manganese spinels and high-rate electrochemical performance of Li[Li0.033Mn1.967]O4. Mater. Renew. Sustain. Energy. 2014. 3: 40–48. DOI: https://doi.org/10.1007/s40243-014-0040-7
  12. Potapenko A.V., Kirillov S.A. Enhancing high-rate electrochemical properties of LiMn2O4 in a LiMn2O4/LiNi0.5Mn1.5O4 core/shell composite. Electrochim. Acta. 2017. 258: 9–16. DOI: https://doi.org/10.1016/j.electacta.2017.10.108