Skip to main content
SpringerLink
Log in

Phase Equilibria in the Li2O–Al2O3–Ni–Co–O System

  • Published:
Inorganic Materials Aims and scope

Abstract—

This paper presents a topological analysis of phase equilibria in the Li2O–Al2O3–Ni–Co–O system. Using the fragmentary experimental data available, we construct isothermal phase diagrams of the Li2O–Al2O3–Nc–O (Nc = Ni + Co) and Li2O–Al2O3–NiO1 + x–CoO1 + x (0 ≤ x < 1) systems. Data are presented on phase equilibria involving Li(Ni,Co,Al)O2 (α-NaFeO2 structure), (Li,Ni,Co,Al)Al2O4 (spinel structure), (Li,Ni,Co)O (rock-salt structure), and (Li,Ni,Co)3O4 (spinel structure) solid solutions, whose homogeneity regions are evaluated.

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.

Fig. 1.
Fig. 2.

Similar content being viewed by others

REFERENCES

  1. Li, W., Liu, X., Celio, H., Smith, P., Dolocan, A., Chi, M., and Manthiram, A., Mn versus Al in layered oxide cathodes in lithium-ion batteries: a comprehensive evaluation on long-term cyclability, Adv. Energ. Mater., 2018, vol. 8, no. 15, paper 703154. https://doi.org/10.1002/aenm.201703154

  2. Wang, Q., Zhang, L., Zhao, P., and Du, Z., Facile synthesis of a high-capacity LiNi0.8Co0.15Al0.05O2 nanoplate cathode with a {010} orientation for lithium-ion batteries, Int. J. Electrochem. Sci., 2018, vol. 13, pp. 10382–10389.https://doi.org/10.20964/2018.11.15

    Article  CAS  Google Scholar 

  3. Purwanto, A., Yudha, C.S., Ubaidillah, U., Widiyandari, H., Ogi, T., and Haerudin, H., NCA cathode material: synthesis methods and performance enhancement efforts, Mater. Res. Express, 2018, vol. 5, paper 122001.https://doi.org/10.1088/2053-1591/aae167

  4. Ding, N., Wang, X., Hou, Y., Wang, S., Li, X., Fam, D.W.H., Zong, Y., and Liu, Z., Rational design of a high-energy LiNi0.8Co0.15Al0.05O2 cathode for Li-ion batteries, Solid State Ionics, 2018, vol. 323, pp. 72–77.https://doi.org/10.1016/j.ssi.2018.05.020

    Article  CAS  Google Scholar 

  5. Liu, W., Qin, M., Gao, C., Yu, D., and Yue, Y., Green and low-cost synthesis of LiNi0.8Co0.15Al0.05O2 cathode material for Li-ion batteries, Mater. Lett., 2019, vol. 246, pp. 153–156.https://doi.org/10.1016/j.matlet.2019.03.064

    Article  CAS  Google Scholar 

  6. Cao, C., Zhang, J., Xie, X., and Xia, B., A novel method for the modification of LiNi0.8Co0.15Al0.05O2 with high cycle stability and low pH, J. Solid State Electrochem., 2019, vol. 23, no. 5, pp. 1351–1358.https://doi.org/10.1007/s10008-019-04216-6

    Article  CAS  Google Scholar 

  7. He, X., Han, G., Lou, S., Du, L., Xu, X., Du, C., Cheng, X., Zuo, P., Ma, Y., Huo, H., and Yin, G., Improved electrochemical performance of LiNi0.8Co0.15Al0.05O2 cathode material by coating of graphene nanodots, J. Electrochem. Soc., 2019, vol. 166, no. 6, pp. A1038–A1044.https://doi.org/10.1149/2.0541906jes

    Article  CAS  Google Scholar 

  8. Liang, M., Sun, Y., Song, D., Shi, X., Han, Y., Zhang, H., and Zhang, L., Superior electrochemical performance of quasi-concentration-gradient LiNi0.8Co0.15Al0.05O2 cathode material synthesized with multi-shell precursor and new aluminum source, Electrochim. Acta, 2019, vol. 300, pp. 426–436.https://doi.org/10.1016/j.electacta.2019.01.125

    Article  CAS  Google Scholar 

  9. Jo, M., Noh, M., Oh, P., Kim, Y., and Cho, J., A new high power LiNi0.81Co0.1Al0.09O2 cathode material for lithium-ion batteries, Adv. Energ. Mater., 2014, vol. 4, no. 13, paper 301583.https://doi.org/10.1002/aenm.201301583

  10. Chen, W., Li, Y., Yang, D., Feng, X., Guan, X., and Mi, L., Controlled synthesis of spherical hierarchical LiNi1 –x–yCoxAlyO2 (0 < x, y < 0.2) via a novel cation exchange process as cathode materials for high-performance lithium batteries, Electrochim. Acta, 2016, vol. 190, pp. 932–938.https://doi.org/10.1016/j.electacta.2016.01.024

    Article  CAS  Google Scholar 

  11. Zhou, P., Meng, H., Zhang, Z., Chen, C., Lu, Y., Cao, J., Cheng, F., and Chen, J., Stable layered Ni-rich LiNi0.9Co0.07Al0.03O2 microspheres assembled with nanoparticles as high-performance cathode materials for lithium-ion batteries, J. Mater. Chem. A, 2017, vol. 5, no. 6, pp. 2724–2731.https://doi.org/10.1039/C6TA09921A

    Article  CAS  Google Scholar 

  12. Cao, H., Xia, B., Xu, N., and Zhang, C., Structural and electrochemical characteristics of Co and Al co-doped lithium nickelate cathode materials for lithium-ion batteries, J. Alloys. Compd., 2004, vol. 376, nos. 1–2, pp. 282–286.https://doi.org/10.1016/j.jallcom.2004.01.008

    Article  CAS  Google Scholar 

  13. Ju, S.H., Kim, J.H., and Kang, Y.C., Electrochemical properties of LiNi0.8Co0.2 –xAlxO2 (0 ≤ x ≤ 0.1) cathode particles prepared by spray pyrolysis from the spray solutions with and without organic additives, Met. Mater. Int., 2010, vol. 16, no. 2, pp. 299–303.https://doi.org/10.1007/s12540-010-0421-0P

    Article  CAS  Google Scholar 

  14. Zhu, X.-J., Liu, H.-X., Gan, X.-Y., Cao, M.-H., Zhou, J., Chen, W., Xu, Q., and Quyang, S.-X., Preparation and characterization of LiNi0.80Co0.20 –xAlxO2 as cathode materials for lithium ion batteries, J. Electroceram., 2006, vol. 17, nos. 2–4, pp. 645–649.https://doi.org/10.1007/s10832-006-6705-6

    Article  CAS  Google Scholar 

  15. Vogler, C., Hemmer, G., Arnold, G., Trépo, A., and Wohlfahrt-Mehrens, M., Lithium nickel oxide Li(Ni0.75Al0.17Co0.08)O2 as cathode material for lithium ion batteries, Ionics, 1999, vol. 5, nos. 5–6, pp. 421–425. https://doi.org/10.1007/BF02376008

    Article  CAS  Google Scholar 

  16. Madhavi, S., Subba Rao, G.V., Chowdari, B.V.R., and Li, S.F.Y., Effect of aluminium doping on cathodic behaviour of LiNi0.7Co0.3O2, J. Power Sources, 2001, vol. 93, pp. 156–162.

    Article  CAS  Google Scholar 

  17. Kalyani, P., Kalaiselvi, N., Renganathan, N.G., and Raghavan, M., Studies on LiNi0.7Al0.3 –xCoxO2 solid solutions as alternative cathode materials for lithium batteries, Mater. Res. Bull., 2004, vol. 39, no. 1, pp. 41–54.https://doi.org/10.1016/j.materresbull.2003.09.021

    Article  CAS  Google Scholar 

  18. Reddy, M.V., Subba Rao, G.V., and Chowdary, B.V.R., Preparation and characterization of LiNi0.5Co0.5O2 and LiNi0.5Co0.4Al0.1O2 by molten salt synthesis for Li ion batteries, J. Phys. Chem. C, 2007, vol. 111, no. 31, pp. 11712–11720.https://doi.org/10.1021/jp0676890

    Article  CAS  Google Scholar 

  19. Chang, Z.-R., Yu, X., Tang, H.-W., Wei, W.-Q., and Dai, D.-M., Influence of Al doping content on the structure and electrochemical properties of LiNi1/3Co2/3xAlxO2, Acta Phys.-Chim. Sin., 2010, vol. 26, no. 3, pp. 567–572.https://doi.org/10.3866/PKU.WHXB20100247

    Article  CAS  Google Scholar 

  20. Castro-García, S., Castro-Couceiro, A., Señarís–Rodríguez, M.A., Soulette, F., and Julien, C., Influence of aluminum doping on the properties of LiCoO2 and LiNi0.5Co0.5O2 oxides, Solid State Ionics, 2003, vol. 156, nos. 1–2, pp. 15–26.https://doi.org/10.1016/S0167-2738(02)00570-2

    Article  Google Scholar 

  21. Adipranoto, D.S., Ishigaki, T., Hoshikawa, A., Iwase, K., Yonemura, M., Mori, K., Kamiyama, Y., Morii, Y., and Hayashi, M., Neutron diffraction studies on structural effect for Ni-doping in LiCo1 −xNixO2, Solid State Ionics, 2014, vol. 262, pp. 92–97.https://doi.org/10.1016/j.ssi.2013.11.014

    Article  CAS  Google Scholar 

  22. Gao, J., Shi, S., Xiao, R., and Li, H., Synthesis and ionic transport mechanisms of α-LiAlO2, Solid State Ionics, 2016, vol, 286, pp. 122–134.https://doi.org/10.1016/j.ssi.2015.12.028

    Article  CAS  Google Scholar 

  23. Dahéron, L., Dedryvère, R., Martinez, H., Flahaut, D., Ménétrier, M., Delmas, C., and Gonbeau, D., Possible explanation for the efficiency of Al-based coatings on LiCoO2: surface properties of LiCo1 – xAlxO2 solid solution, Chem. Mater., 2009, vol. 21, no. 23, pp. 5607–5616.https://doi.org/10.1021/cm901972e

    Article  CAS  Google Scholar 

  24. Shinova, E., Zhecheva, E., and Stoyanova, R., Formation of LiAlyNi1 –yO2 solid solutions under high and atmospheric pressure, J. Solid State Chem., 2006, vol. 179, no. 10, pp. 3151–3158.https://doi.org/10.1016/j.jssc.2006.06.011

    Article  CAS  Google Scholar 

  25. Tamura, A., Takai, S., Yabutsuka, T., and Yao, T., Relaxation analysis of LixNiO2 and Lix(NCA)O2 in the deeply lithium extracted region (x ≤ 0.12), J. Electrochem. Soc., 2017, vol. 167, no. 7, pp. A1514–A1519.https://doi.org/10.1149/2.0691707jes

    Article  CAS  Google Scholar 

  26. Kang, J., Takai, S., Yabutsuka, T., and Yao, T., Structural relaxation of Lix(Ni0.874Co0.090Al0.036)O2 after lithium extraction down to x = 0.12, Materials, 2018, vol. 11, no. 9, paper 1299.https://doi.org/10.3390/ma11081299

  27. Konar, B., Van Ende, M.-A., and Jung, I.-H., Critical evaluation and thermodynamic optimization of the Li2O–Al2O3 and Li2O–MgO–Al2O3 systems, Metall. Mater. Trans. B, 2018, vol. 49, no. 7, pp. 2917–2944.https://doi.org/10.1007/s11663-018-1349-x

    Article  CAS  Google Scholar 

  28. Gomes, K.Q., Bacelos, M., and Filho, P.I.P., Quantification of phase compositions in the system [(NiO)x] ∙ [(CoO)1 –x] ∙ [(Al2O3)], 0.05 ≤ x ≤ 0.95, and the effect in the electrical properties of semiconductor as a consequence of the CO+2 variation, Mater. Sci. Forum., 2012, vols. 727–728, pp. 550–555. https://doi.org/10./14028/www.scientific.net/MSF.727-728.550

    Article  Google Scholar 

  29. Pan, D., Yuan, D., Sun, H., Duan, X., Luan, C., Guo, S., Li, Z., and Wang, L., Preparation and characterization of Co2+-doped LiAl5O8 nano-crystal powders by sol–gel technique, Mater. Chem. Phys., 2006, vol. 96, pp. 317–320.https://doi.org/10.1016/j.matchemphys.2005.07.020

    Article  CAS  Google Scholar 

  30. Raj, C.J., Lincoln, M.B., and Das, S.J., Synthesis and characterization of doped lithium aluminate nanocrystalline particles by sol–gel method, Cryst. Res. Technol., 2008, vol. 43, no. 8, pp. 823–827.https://doi.org/10.1002/crat.200811165

    Article  CAS  Google Scholar 

  31. Kaboon, S. and Hu, Y.H., Study of NiO–CoO and Co3O4–Ni3O4 solid solutions in multiphase Ni–Co–O systems, Ind. Eng. Chem. Res., 2011, vol. 50, no. 4, pp. 2015–2020.https://doi.org/10.1021/ie101249r

    Article  CAS  Google Scholar 

  32. Li, Y., Han, X., Yi, T., He, Y., and Li, X., Review and prospect of NiCo2O4-based composite materials for supercapacitor electrodes, J. Energy Chem., 2019, vol. 31, pp. 54–78.https://doi.org/10.1016/j.jechem.2018.05.010

    Article  Google Scholar 

  33. Peña, O., Bodenez, V., Guixouarn, T., Meza, E., and Gautier, J.L., Magnetic properties of lithium-based spinels Li(NixCo2 –x)O4, J. Magn. Magn. Mater., 2004, vols. 272–276, pp. E1579–1580.https://doi.org/10.1016/j.jmmm.2003.12.813

    Article  CAS  Google Scholar 

  34. Antolini, E., LixNi1 –xO (0 < x ≤ 0.3) solid solutions: formation, structure and transport properties, Mater. Chem. Phys., 2003, vol. 82, no. 3, pp. 937–948.https://doi.org/10.1016/j.matchemphys.2003.08.006

    Article  CAS  Google Scholar 

  35. Wu, Y., Pasero, D., McCabe, E.E., Matsushima, Y., and West, A.R., Formation of disordered and partially ordered LixCo1 –xO, J. Mater. Chem., 2009, vol. 19, no. 10, pp. 1443–1448.https://doi.org/10.1039/b816486j

    Article  CAS  Google Scholar 

  36. Kazenas, E.K. and Tsvetkov, Yu.V., Termodinamika ispareniya oksidov (Thermodynamics of Oxide Vaporization), Moscow: URSS, 2015.

Download references

Funding

This work was supported by the Russian Federation Ministry of Science and Higher Education: state research target for the Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences; basic research.

Author information

Authors and Affiliations

  1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, 119991, Moscow, Russia

    G. D. Nipan

  2. AkKo Lab, ul. Gilyarovskogo 65/1, 129110, Moscow, Russia

    D. Yu. Kornilov

Authors
  1. G. D. Nipan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. D. Yu. Kornilov
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to G. D. Nipan.

Additional information

Translated by O. Tsarev

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Nipan, G.D., Kornilov, D.Y. Phase Equilibria in the Li2O–Al2O3–Ni–Co–O System. Inorg Mater 56, 809–814 (2020). https://doi.org/10.1134/S0020168520070110

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0020168520070110

Keywords:

Search

Navigation