Details
| Original language | English |
|---|---|
| Pages (from-to) | 15192-15202 |
| Number of pages | 11 |
| Journal | Journal of Physical Chemistry C |
| Volume | 116 |
| Issue number | 29 |
| Publication status | Published - 26 Jul 2012 |
Abstract
Various polycrystalline samples of Al-doped garnet-like Li 7La 3Zr 2O 12 crystallizing with cubic symmetry were synthesized from the binary oxides Li 2O, ZrO 2, Al 2O 3, and La 2O 3. The synthesis of phase pure samples was carried out following a two-step preparation route. It consists of an activation step by high-energy ball milling and a subsequent annealing step at elevated temperatures. The synthesis route chosen allows the precise adjustment of the cationic ratios, leading to a garnet which is best described by the formula Li 7-3x+zAl x+y+zLa 3-yZr 2-zO 12. As confirmed by X-ray powder diffraction and 27Al magic angle spinning nuclear magnetic resonance (NMR), at low Al concentrations the incorporated Al 3+ ions act as an aliovalent dopant by replacing three Li + ions. However, with increasing Al content, La 3+ and Zr 4+ ions are progressively replaced by Al ions. It turned out that, in particular, the substitution of La 3+ and Zr 4+ with Al 3+ ions stabilizes the cubic modification of the garnet and greatly affects the corresponding Li ion dynamics. The latter has been probed by both impedance and 7Li NMR spectroscopy. The high ion conductivity (10 -4 S cm -1 at 293 K) found does not only depend on the stoichiometry and the annealing conditions chosen but also on the exact kind of Al distribution on the different sites in Li 7La 3Zr 2O 12.
ASJC Scopus subject areas
- Materials Science(all)
- Electronic, Optical and Magnetic Materials
- Energy(all)
- General Energy
- Chemistry(all)
- Physical and Theoretical Chemistry
- Materials Science(all)
- Surfaces, Coatings and Films
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In: Journal of Physical Chemistry C, Vol. 116, No. 29, 26.07.2012, p. 15192-15202.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Mechanosynthesis of solid electrolytes
T2 - Preparation, characterization, and li ion transport properties of garnet-type Al-doped Li 7La 3Zr 2O 12 crystallizing with cubic symmetry
AU - Düvel, Andre
AU - Kuhn, Alexander
AU - Robben, Lars
AU - Wilkening, Martin
AU - Heitjans, Paul
PY - 2012/7/26
Y1 - 2012/7/26
N2 - Various polycrystalline samples of Al-doped garnet-like Li 7La 3Zr 2O 12 crystallizing with cubic symmetry were synthesized from the binary oxides Li 2O, ZrO 2, Al 2O 3, and La 2O 3. The synthesis of phase pure samples was carried out following a two-step preparation route. It consists of an activation step by high-energy ball milling and a subsequent annealing step at elevated temperatures. The synthesis route chosen allows the precise adjustment of the cationic ratios, leading to a garnet which is best described by the formula Li 7-3x+zAl x+y+zLa 3-yZr 2-zO 12. As confirmed by X-ray powder diffraction and 27Al magic angle spinning nuclear magnetic resonance (NMR), at low Al concentrations the incorporated Al 3+ ions act as an aliovalent dopant by replacing three Li + ions. However, with increasing Al content, La 3+ and Zr 4+ ions are progressively replaced by Al ions. It turned out that, in particular, the substitution of La 3+ and Zr 4+ with Al 3+ ions stabilizes the cubic modification of the garnet and greatly affects the corresponding Li ion dynamics. The latter has been probed by both impedance and 7Li NMR spectroscopy. The high ion conductivity (10 -4 S cm -1 at 293 K) found does not only depend on the stoichiometry and the annealing conditions chosen but also on the exact kind of Al distribution on the different sites in Li 7La 3Zr 2O 12.
AB - Various polycrystalline samples of Al-doped garnet-like Li 7La 3Zr 2O 12 crystallizing with cubic symmetry were synthesized from the binary oxides Li 2O, ZrO 2, Al 2O 3, and La 2O 3. The synthesis of phase pure samples was carried out following a two-step preparation route. It consists of an activation step by high-energy ball milling and a subsequent annealing step at elevated temperatures. The synthesis route chosen allows the precise adjustment of the cationic ratios, leading to a garnet which is best described by the formula Li 7-3x+zAl x+y+zLa 3-yZr 2-zO 12. As confirmed by X-ray powder diffraction and 27Al magic angle spinning nuclear magnetic resonance (NMR), at low Al concentrations the incorporated Al 3+ ions act as an aliovalent dopant by replacing three Li + ions. However, with increasing Al content, La 3+ and Zr 4+ ions are progressively replaced by Al ions. It turned out that, in particular, the substitution of La 3+ and Zr 4+ with Al 3+ ions stabilizes the cubic modification of the garnet and greatly affects the corresponding Li ion dynamics. The latter has been probed by both impedance and 7Li NMR spectroscopy. The high ion conductivity (10 -4 S cm -1 at 293 K) found does not only depend on the stoichiometry and the annealing conditions chosen but also on the exact kind of Al distribution on the different sites in Li 7La 3Zr 2O 12.
UR - http://www.scopus.com/inward/record.url?scp=84864197273&partnerID=8YFLogxK
U2 - 10.1021/jp301193r
DO - 10.1021/jp301193r
M3 - Article
AN - SCOPUS:84864197273
VL - 116
SP - 15192
EP - 15202
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 29
ER -