Investigation on the Arrangement of Lithium Ions in LixLa1/3NbO3 with Perovskite Structure
- 8 July 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry B
- Vol. 109 (30), 14648-14653
- https://doi.org/10.1021/jp052142r
Abstract
The relationship between the Li arrangement and the electrochemical behavior has been examined as a function of composition x in electrochemically lithiated A-site deficient perovskite, LixLa1/3NbO3. The cell potential diagram and powder X-ray diffraction (XRD) study indicated that the Li ions are inserted into the vacant Perovskite A-site with an electrochemical reaction. In addition, the derivatives of the cell potential diagram showed three cathodic peaks, indicating a stepwise Li insertion mechanism takes place. Such a stepwise behavior would be ascribed to the changes in arrangement of inserted Li ions in the Perovskite lattice, since the XRD patterns of pristine La1/3NbO3 showed that the La arrangement in La1/3NbO3 was ordered along the c-axis, causing two kinds of A-site vacancies. To reveal the changes in the arrangement of Li ions, the entropy measurement of the reaction was performed by both the electrochemical and the calorimetric techniques. Moreover, the formation energy of the Perovskite structure with various Li arrangements was compared by using an ab initio calculation. The results of experiment and computation suggested that the electrochemical reaction proceeded via two kinds of superstructures of Li1/6La1/3NbO3 and Li1/2La1/3NbO3 due to the ordered arrangement of Li ions.Keywords
This publication has 20 references indexed in Scilit:
- Changes in electronic structure upon lithium insertion reaction into the A-site deficient perovskite type oxides, Gd1/3TaO3Solid State Ionics, 2004
- Study on the AC Impedance Spectroscopy for the Li Insertion Reaction of LixLa1/3NbO3 at the Electrode−Electrolyte InterfaceThe Journal of Physical Chemistry B, 2003
- Heats of mixing and of entropy in porous insertion electrodesJournal of Power Sources, 2003
- Using X-ray Absorption Spectroscopy to Measure Changes of Electronic Structure Accompanying Lithium Insertion into the Perovskite Type OxidesChemistry of Materials, 2003
- Electrochemical Lithium Insertion for Perovskite Oxides of LiyLa(1-y)/3NbO3 (y = 0, 0.1, 0.25)The Journal of Physical Chemistry B, 2002
- Hollandite cathodes for lithium ion batteries. 2. Thermodynamic and kinetics studies of lithium insertion into BaMMn7O16 (M=Mg, Mn, Fe, Ni)Electrochimica Acta, 2001
- Thermodynamic and kinetic approaches to lithium intercalation into a Li1−δMn2O4 electrode using Monte Carlo simulationElectrochimica Acta, 2001
- Measurement of the Entropy of Reaction as a Function of State of Charge in Doped and Undoped Lithium Manganese OxideJournal of the Electrochemical Society, 2001
- Ionic conduction of lithium for Perovskite-type compounds, Li x La (1− x )/3 NbO 3 and (Li 0.25 La 0.25 ) 1− x Sr 0.5 x NbO 3Journal of Solid State Electrochemistry, 1998
- Full-potential, linearized augmented plane wave programs for crystalline systemsComputer Physics Communications, 1990