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LiNi1 − x − y Co x Mn y O2 (x = y = 0.1, 0.2, 0.33) cathode materials prepared using mechanical activation: Structure, state of ions, and electrochemical performance

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Abstract

We have investigated LiNi1 − x − y Co x Mn y O2 (x = y = 0.1, 0.2, 0.33) cathode materials synthesized from mechanically activated mixtures of lithium hydroxide and nickel cobalt manganese hydroxide. The materials have a layered structure (sp. gr. \(R\bar 3m\)). Their unit-cell volume and the degree of disordering in their structure decrease with decreasing nickel content. According to x-ray photoelectron spectroscopy data, the major states of the transition-metal ions in the surface layer of the materials are Ni2+, Co3+, and Mn4+. With increasing nickel content, the Ni 2p 3/2 and Co 2p 3/2 binding energies increase, attesting to changes in M-O bond covalence. The highest specific electrochemical capacity, ∼170 mA h/g, is offered by LiNi0.6Co0.2Mn0.2O2. The position of redox peaks in the differential capacity curves of the three materials depends on composition: with increasing nickel content, the peaks shift to lower voltages.

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References

  1. Yabuuchi, N. and Ohzuku, T., Novel Lithium Insertion Material of LiCo1/3Ni1/3Mn1/3O2 for Advanced Lithium-Ion Batteries, J. Power Sources, 2003, vols. 119–121, pp. 171–174.

    Article  Google Scholar 

  2. Koyama, Y., Makimura, Y., Tanaka, I., et al., Systematic Research on Insertion Materials Based on Superlattice Models in a Phase Triangle of LiCoO2-LiNiO2-LiMnO2: I. First-Principles Calculation on Electronic and Crystal Structures, Phase Stability and New LiNi1/2Mn1/2O2 Material, J. Electrochem. Soc., 2004, vol. 151, no. 9, pp. A1499–A1506.

    Article  CAS  Google Scholar 

  3. Koyama, Y., Yabuuchi, N., Tanaka, I., et al., Solid-State Chemistry and Electrochemistry of LiCo1/3Ni1/3Mn1/3O2 for Advanced Lithium-Ion Batteries: I. First-Principles Calculation on the Crystal and Electronic Structures, J. Electrochem. Soc., 2004, vol. 151, no. 10, pp. A1545–A1551.

    Article  CAS  Google Scholar 

  4. Yabuuchi, N., Koyama, Y., Nakayama, N., and Ohzuku, T., Solid-State Chemistry and Electrochemistry of LiCo1/3Ni1/3Mn1/3O2 for Advanced Lithium-Ion Batteries: II. Preparation and Characterization, J. Electrochem. Soc., 2005, vol. 152, no. 7, pp. A1434–A1440.

    Article  CAS  Google Scholar 

  5. Jiang, J., Eberman, K.W., Krause, L.J., and Dahn, J.R., Structure, Electrochemical Properties, and Thermal Stability Studies of Cathode Materials in the xLi[Mn1/2Ni1/2]O2 · yLiCoO2 · zLi[Li1/3Mn2/3]O2 Pseudoternary System (x + y + z = 1), J. Electrochem. Soc., 2005, vol. 152, no. 9, pp. A1879–A1889.

    Article  CAS  Google Scholar 

  6. Ngala, J.K., Chernova, N.A., Ma, M., et al., The Synthesis, Characterization, and Electrochemical Behavior of the Layered LiNi0.4Mn0.4Co0.2O2, J. Mater. Chem., 2004, vol. 14, pp. 214–220.

    Article  CAS  Google Scholar 

  7. Tran, N., Croguennec, L., Jordy, C., et al., Influence of the Synthesis Route on the Electrochemical Properties of LiNi0.425Mn0.425Co0.15O2, Solis State Ionics, 2005, vol. 176, pp. 1539–1547.

    Article  CAS  Google Scholar 

  8. Liao, P.Y., Duh, J.G., and Sheen, S.R., Effect of Mn Content on the Microstructure and Electrochemical Performance of LiNi0.75 − x Co0.25Mn x O2 Cathode Materials, J. Electrochem. Soc., 2005, vol. 152, no. 9, pp. A1695–A1700.

    Article  CAS  Google Scholar 

  9. Cao, H., Zhang, Y., Zhang, J., and Xia, B., Synthesis and Electrochemical Characteristics of Layered LiNi0.6Co0.2Mn0.2O2 Cathode Material for Lithium Ion Batteries, Solid State Ionics, 2005, vol. 176, pp. 1207–1211.

    Article  CAS  Google Scholar 

  10. Liu, Z., Yu, A., and Lee, J.Y., Synthesis and Characterization of LiNi1 − x − y Co x Mn y O2 as the Cathode Materials of Secondary Lithium Batteries, J. Power Sources, 1999, vols. 81–82, pp. 416–419.

    Article  Google Scholar 

  11. Cho, J., Kim, T.-J., Kim, J., et al., Synthesis, Thermal, and Electrochemical Properties of AlPO4-Coated LiNi0.8Co0.1Mn0.1O2 Cathode Materials for a Li-Ion Cell, J. Electrochem. Soc., 2004, vol. 151, no. 11, pp. A1899–A1904.

    Article  CAS  Google Scholar 

  12. Avvakumov, E., Senna, M., and Kosova, N., Soft Mechanochemical Synthesis. A Basics for New Chemical Technologies, Dordrecht: Kluwer, 2001.

    Google Scholar 

  13. Guerlou-Demourgues, L., Denage, C., and Delmas, C., New Manganese-Substituted Nickel Hydroxides: Part 1. Crystal Chemistry and Physical Characterization, J. Power Sources, 1994, vol. 52, pp. 269–274.

    Article  CAS  Google Scholar 

  14. Eikhler, V.V., Lukashenko, A.I., Makukha, V.K., and Kosova, N.V., Automatic System for Cycling Electrochemical Cells, Elektrokhim. Energ., 2005, vol. 5, no. 2, pp. 135–138.

    Google Scholar 

  15. Julien, C., Local Structure and Electrochemistry of Lithium Cobalt Oxides and Their Doped Compounds, Solid State Ionics, 2003, vol. 157, pp. 57–71.

    Article  CAS  Google Scholar 

  16. Kosova, N., Devyatkina, E., and Kaichev, V., Structural and Electronic Properties of Layered LiNi1 − x Mn x O2 Prepared Using Mechanical Activation, in Lithium Battery Discussion: Electrode Materials, Bordeaux: Arcachon, 2005, pp. 50–51.

    Google Scholar 

  17. McIntyre, N.S. and Cook, M.G., X-ray Photoelectron Studies on Some Oxides and Hydroxides of Cobalt, Nickel, and Copper, Anal. Chem., 1975, vol. 47, pp. 2208–2213.

    Article  CAS  Google Scholar 

  18. Li, C.P., Proctor, A., and Hercules, D.M., Curve Fitting Analysis of ESCA Ni 2p Spectra of Nickel-Oxygen Compounds and Ni/Al2O3 Catalysts, Appl. Spectrosc., 1984, vol. 38, pp. 880–886.

    Article  CAS  Google Scholar 

  19. Shaju, K.M., Subba Rao, G.V., and Chowdari, B.V.R., X-ray Photoelectron Spectroscopy and Electrochemical Behaviour of 4 V Cathode, Li(Ni1/2Mn1/2)O2, Electrochim. Acta, 2003, vol. 48, pp. 1505–1514.

    Article  CAS  Google Scholar 

  20. Carley, A.F., Jackson, S.D., Shea, J.N., and Roberts, M.W., The Formation and Characterization of Ni3+—An X-ray Photoelectron Spectroscopic Investigation of Potassium-Doped Ni(110)-O, Surf. Sci., 1999, vol. 440, pp. L868–L874.

    Article  CAS  Google Scholar 

  21. Amine, K., Tukamoto, H., Yasuda, H., and Fujita, Y., A New Three-Volt Spinel Li1 + x Mn1.5Ni0.5O4 for Secondary Lithium Batteries, J. Electrochem. Soc., 1996, vol. 143, pp. 1607–1613.

    Article  CAS  Google Scholar 

  22. Montoro, L.A., Abbate, M., Almeida, E.C., and Rosolen, J.M., Electronic Structure of the Transition Metal Ions in LiCoO2, LiNiO2, and LiCo0.5Ni0.5O2, Chem. Phys. Lett., 1999, vol. 309, pp. 14–18.

    Article  CAS  Google Scholar 

  23. Shaju, K.M., Subba Rao, G.V., and Chowdari, B.V.R., Performance of Layered Li(Ni1/3Co1/3Mn1/3)O2 as Cathode for Li-Ion Batteries, Electrochim. Acta, 2003, vol. 48, pp. 145–151.

    Article  Google Scholar 

  24. Oku, M., Hirokawa, K., and Ikeda, S., X-ray Photoelectron Spectroscopy of Manganese-Oxygen Systems, J. Electron Spectrosc. Relat. Phenom., 1975, vol. 7, pp. 465–473.

    Article  CAS  Google Scholar 

  25. Kosova, N.V., Kaichev, V.V., Bukhtiyarov, V.I., et al., Electronic State of Cobalt and Oxygen Ions in Stoichiometric and Nonstoichiometric Li1 + x CoO2 before and after Delithiation according to XPS and DRS, J. Power Sources, 2003, vols. 119–121, pp. 669–673.

    Article  Google Scholar 

  26. Sun, Y., Ouyang, C., Wang, Z., et al., Effect of Co Content on Rate Performance of LiMn0.5 − x Co x Ni0.5 − x O2 Cathode Materials for Lithium-Ion Batteries, J. Electrochem. Soc., 2004, vol. 151, pp. A504–A508.

    Article  CAS  Google Scholar 

  27. Hwang, B.J., Tsai, Y.W., Chen, C.H., and Santhanam, R., Influence of Mn Content on the Morphology and Electrochemical Performance of LiNi1 − x − y Co x Mn y O2 Cathode Materials, J. Mater. Chem., 2003, vol. 13, pp. 1962–1968.

    Article  CAS  Google Scholar 

  28. Kuiper, P., Kruizinga, G., Ghijsen, J., et al., Character of Holes in Li x Ni1 − x O2 and Their Magnetic Behavior, Phys. Rev. Lett., 1989, vol. 62, pp. 221–224.

    Article  CAS  Google Scholar 

  29. Bukhtiyarov, V.I., Hävecker, M., Kaichev, V.V., et al., The Nature of Atomic Oxygen Species on Silver: Photoelectron Spectroscopy and X-ray Absorption Studies, Phys. Rev. B: Condens. Matter Mater. Phys., 2003, vol. 67, no. 23, p. 235422.

    Google Scholar 

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Authors and Affiliations

  1. Institute of Solid-State Chemistry and Mechanochemistry, Siberian Division, Russian Academy of Sciences, ul. Kutateladze 18, Novosibirsk, 630128, Russia

    N. V. Kosova & E. T. Devyatkina

  2. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, pr. Akademika Lavrent’eva 5, Novosibirsk, 630090, Russia

    V. V. Kaichev

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  1. N. V. Kosova
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  2. E. T. Devyatkina
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  3. V. V. Kaichev
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Original Russian Text © N.V. Kosova, E.T. Devyatkina, V.V. Kaichev, 2007, published in Neorganicheskie Materialy, 2007, Vol. 43, No. 2, pp. 227–235.

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Kosova, N.V., Devyatkina, E.T. & Kaichev, V.V. LiNi1 − x − y Co x Mn y O2 (x = y = 0.1, 0.2, 0.33) cathode materials prepared using mechanical activation: Structure, state of ions, and electrochemical performance. Inorg Mater 43, 185–193 (2007). https://doi.org/10.1134/S0020168507020161

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  • DOI: https://doi.org/10.1134/S0020168507020161

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