Journal of Materials Science

, Volume 42, Issue 10, pp 3343–3348 | Cite as

EPR analysis of the local structure of Ni3+ ions in Ni-based electrode materials obtained under high-pressure

  • Ekaterina ZhechevaEmail author
  • Radostina Stoyanova
  • Elitza Shinova
Size-Dependent Effects


X-band and high-frequency EPR spectroscopy was applied to monitor the short-range cation ordering in Ga, Al and Li substituted LiNiO2 with a layered crystal structure. The mixed oxides were obtained by a high-pressure synthesis in an oxygen rich atmosphere. Analysis of the EPR line-width from the X-band experiments together with the values of the g-tensor from the high-frequency EPR experiments permits assesing the local structure of the mixed metal layers. The results obtained show that LiGayNi1−yO2, LiAlyNi1−yO2 and Li1 + xNi1−xO2 are homogeneous solid solutions, whereas the Li1 + xNi1−xyAlyO2 compositions have rather a complex domain structure of the type (1−a)LiAlyNi1−yO2.aLi[Li1/3Ni2/3]O2.


Electron Paramagnetic Resonance Electron Paramagnetic Resonance Spectrum Electron Paramagnetic Resonance Signal Electron Paramagnetic Resonance Spectroscopy Li2TiO3 



The authors thank the National Science Fund of Bulgaria (Contract no. Ch1304/2003) for financial support. R.S. and E.Sh. are grateful to the EC for a grant of a EU “Research Infrastructures: Transnational Access” Programme (Contract No. 505320 (RITA) – High Pressure) for performing high-pressure synthesis experiments at the Bayrisches Geoinstitute. The high-frequency EPR measurements carried out at High Magnetic Field Laboraty in Grenoble, France, were supported by the European Commission within the 6th framework programme “Transnational Access - Specific Support Action” (contract No. RITA-CT-2003-505474) – “Access to research in very high magnetic field”. The authors are very grateful to Dr. T. Boffa-Ballaran and Dr. C. McCammon, from Bayerisches Geoinstitut, Universität Bayreuth, and Dr. A.-L. Barra, from High Magnetic Field Laboratory in Grenoble, for their help.


  1. 1.
    Brousesely M, Biensan P, Simon B (1999) Electrochim Acta 45:3CrossRefGoogle Scholar
  2. 2.
    Delmas C, Menetrier M, Croguennec L, Saadoune I, Rougier A, Poillerie C, Prado G, Grüne M, Fournes L (1999) Electrochim Acta 145:243CrossRefGoogle Scholar
  3. 3.
    Alcántara R, Lavela P, Tirado J-L, Zhecheva E, Stoyanova R (1999) J Solid State Electrochem 3:121Google Scholar
  4. 4.
    Whittingham MS (2004) Chem Rev 104:4271CrossRefGoogle Scholar
  5. 5.
    Grey CP, Dupre N (2004) Chem Rev 104:4493CrossRefGoogle Scholar
  6. 6.
    Julien CM, Massot M, Poinsignon C (2004) Spectrochim Acta A 60:689CrossRefGoogle Scholar
  7. 7.
    Alcántara R, Lavela P, Pérez-Vicente C, Tirado JL, Jumas JC, Olivier-Fourcade J (2000) Solid State Commun 115:115CrossRefGoogle Scholar
  8. 8.
    Stoyanova R, Zhecheva E, Alcántara R, Tirado JL, Bromiley G, Bromiley F, Boffa Ballaran T (2004) J Mater Chem 14:363CrossRefGoogle Scholar
  9. 9.
    Shinova E, Zhecheva E, Stoyanova R, Bromiley G (2005) J Solid State Chem 178:1661CrossRefGoogle Scholar
  10. 10.
    Shinova E, Zhecheva E, Stoyanova R, Bromiley GD, Alcántara R, Tirado JL (2005) J Solid State Chem 178:2692CrossRefGoogle Scholar
  11. 11.
    Stoyanova R, Zhecheva E, Friebel C (1993) J Phys Chem Solids 54:9CrossRefGoogle Scholar
  12. 12.
    Stoyanova R, Zhecheva E, Friebel C (1994) Solid State Ionics 73:1CrossRefGoogle Scholar
  13. 13.
    Van Vleck JH (1948) Phys Rev 74:1168CrossRefGoogle Scholar
  14. 14.
    Anderson PW, Weiss PR (1953) Rev Mod Phys 25:269CrossRefGoogle Scholar
  15. 15.
    Morya T (1956) Prog Theor Phys Kyoto 16:23CrossRefGoogle Scholar
  16. 16.
    Stoyanova R, Zhecheva E, Alcántara R, Lavela P, Tirado JL (1997) Solid State Commun 102:457CrossRefGoogle Scholar
  17. 17.
    Anderson KK, Barra AL (2002) Spectrochim Acta A 58:1101CrossRefGoogle Scholar
  18. 18.
    Kim J-S, Johnson CS, Vaughey JT, Thackeray MM, Hackney SA, Yoon W, Grey CP (2004) Chem Mater 16:1996CrossRefGoogle Scholar
  19. 19.
    Yoon W-S, Iannopollo S, Grey CP, Carlier D, Gorman J, Reed J, Ceder G (2004) Electrochem Solid-State Lett 7:A167CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2007

Authors and Affiliations

  • Ekaterina Zhecheva
    • 1
    Email author
  • Radostina Stoyanova
    • 1
  • Elitza Shinova
    • 1
  1. 1.Institute of General and Inorganic ChemistryBulgarian Academy of SciencesSofiaBulgaria

Personalised recommendations