Layered solid solutions of LiNi1-xCoxO2 with alpha-LiGaO2 obtained under high oxygen pressure

R Stoyanova*, E Zhecheva, R Alcantara, JL Tirado, G Bromiley, F Bromiley, TB Ballaran

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Solid solutions in the alpha-LiGaO2 - LiNiO2 system were prepared over the whole concentration range under high pressure (3 GPa) at 700 degreesC in oxygen-rich atmosphere. The structure of LiGayNi1-yO2 solid solutions was characterized by XRD analysis, EPR and IR spectroscopy. It was found that Ga substitutes for Ni in the NiO2 layer (3a site), while Li and O are in their normal positions (3b and 6c, respectively). The occupancy of Ni in the Li site is negligible for Ga-substituted oxides. The progressive replacement of Ni by Ga leads to an unusual concentration variation of the a-parameter: at 10% Ga additives, there is a contraction of the a-parameter together with the expansion of the c-parameter. The concentration variation of the a-parameter can be related to increased trigonal distortion of GayNi1-yO2 layers upon Ga substitution. The electrochemical performance of LiGay(Ni1-xCox)(1-y)O-2 solid solutions as a cathode material in lithium ion cells has been evaluated in potentiostatic experiments. During the first charge, there is an irreversible peak at about 4.7 V, which was compared with the electrochemical Li extraction from layered oxides characterized with a partial mixing of lithium and metal ions in the metal layers. After the first charge, a reversible electrochemical intercalation of Li is achieved. The effect of Ga on the potential of lithium extraction/insertion in LiGay(Ni1-xCox)(1-y)O-2 was discussed.

Original languageEnglish
Pages (from-to)366-373
Number of pages8
JournalJournal of Materials Chemistry
Volume14
Issue number3
DOIs
Publication statusPublished - 2004

Keywords

  • RECHARGEABLE LITHIUM BATTERIES
  • ION SHUTTLECOCK BATTERIES
  • X-RAY-DIFFRACTION
  • CATHODE MATERIALS
  • STRUCTURAL-CHARACTERIZATION
  • ELECTROCHEMICAL PROPERTIES
  • ELECTRODE MATERIALS
  • CRYSTAL-STRUCTURE
  • LIAL1/4NI3/4O2 R(3)OVER-BAR-M
  • INSERTION ELECTRODES

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