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A synthesis and crystal chemical study of the fast ion conductor Li(7-3x)Ga(x)La3 Zr2O12 with x = 0.08 to 0.84.

Rettenwander D, Geiger CA, Tribus M, Tropper P, Amthauer G - Inorg Chem (2014)

Bottom Line: The unit-cell parameter, a0, of the various garnets does not vary significantly as a function of Ga(3+) content, with a value of about 12.984(4) Å.Full chemical analyses for the solid solutions were obtained giving: Li7.08Ga0.06La2.93Zr2.02O12, Li6.50Ga0.15La2.96Zr2.05O12, Li6.48Ga0.23La2.93Zr2.04O12, Li5.93Ga0.36La2.94Zr2.01O12, Li5.38Ga0.53La2.96Zr1.99O12, Li4.82Ga0.60La2.96Zr2.00O12, and Li4.53Ga0.72La2.94Zr1.98O12.The NMR spectra are interpreted as indicating that Ga(3+) mainly occurs in a distorted 4-fold coordinated environment that probably corresponds to the general 96h crystallographic site of garnet.

View Article: PubMed Central - PubMed

Affiliation: Department of Materials Science and Physics, University of Salzburg , Hellbrunnerstrasse 34, A-5020 Salzburg, Austria.

ABSTRACT
Fast-conducting phase-pure cubic Ga-bearing Li7La3Zr2O12 was obtained using solid-state synthesis methods with 0.08 to 0.52 Ga(3+) pfu in the garnet. An upper limit of 0.72 Ga(3+) pfu in garnet was obtained, but the synthesis was accompanied by small amounts of La2Zr2O12 and LiGaO3. The synthetic products were characterized by X-ray powder diffraction, electron microprobe and SEM analyses, ICP-OES measurements, and (71)Ga MAS NMR spectroscopy. The unit-cell parameter, a0, of the various garnets does not vary significantly as a function of Ga(3+) content, with a value of about 12.984(4) Å. Full chemical analyses for the solid solutions were obtained giving: Li7.08Ga0.06La2.93Zr2.02O12, Li6.50Ga0.15La2.96Zr2.05O12, Li6.48Ga0.23La2.93Zr2.04O12, Li5.93Ga0.36La2.94Zr2.01O12, Li5.38Ga0.53La2.96Zr1.99O12, Li4.82Ga0.60La2.96Zr2.00O12, and Li4.53Ga0.72La2.94Zr1.98O12. The NMR spectra are interpreted as indicating that Ga(3+) mainly occurs in a distorted 4-fold coordinated environment that probably corresponds to the general 96h crystallographic site of garnet.

No MeSH data available.


71Ga MAS NMR spectra of Li7–3xGa3+xLa3Zr2O12 garnets with xint = 0.08–0.84.Asterisks (*) mark spinning side bands. Thespectra on the right are shown over a smaller range of chemical shiftvalues. The spectrum shown in red is simulated for the sample with xint = 0.36.
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fig5: 71Ga MAS NMR spectra of Li7–3xGa3+xLa3Zr2O12 garnets with xint = 0.08–0.84.Asterisks (*) mark spinning side bands. Thespectra on the right are shown over a smaller range of chemical shiftvalues. The spectrum shown in red is simulated for the sample with xint = 0.36.

Mentions: Spectra for the sampleswith xint = 0.16, 0.24, 0.36, 0.54, 0.64,and 0.84 are shown in Figure 5. 71Ga (spin quantum number I = 3/2, natural abundance39.6%) is a quadrupole nucleus; the interaction of its rather largequadrupole moment (Q = 10.7 × 10–30 m2) with the surrounding electric field gradient resultsin a central line that is perturbed by second-order effects. Theirshape can be simulated well with a single set of NMR parameters, namelyan isotropic chemical shift, δ, of 244(2) ppm, a quadrupolarcoupling constant, CQ, of 4.0(2) MHz,and an asymmetry parameter, ηQ, of 0.46(3). The spectrumof the sample with xint = 0.84, whichhas a slightly different line shape than those in the spectra of theother garnets (Figure 5), also has a NMR resonancewith the major component at δ = 244(2) ppm. The spectra forsamples with Ga3+ contents, xint ≥ 0.36, show the best signal to background ratios.


A synthesis and crystal chemical study of the fast ion conductor Li(7-3x)Ga(x)La3 Zr2O12 with x = 0.08 to 0.84.

Rettenwander D, Geiger CA, Tribus M, Tropper P, Amthauer G - Inorg Chem (2014)

71Ga MAS NMR spectra of Li7–3xGa3+xLa3Zr2O12 garnets with xint = 0.08–0.84.Asterisks (*) mark spinning side bands. Thespectra on the right are shown over a smaller range of chemical shiftvalues. The spectrum shown in red is simulated for the sample with xint = 0.36.
© Copyright Policy
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4061145&req=5

fig5: 71Ga MAS NMR spectra of Li7–3xGa3+xLa3Zr2O12 garnets with xint = 0.08–0.84.Asterisks (*) mark spinning side bands. Thespectra on the right are shown over a smaller range of chemical shiftvalues. The spectrum shown in red is simulated for the sample with xint = 0.36.
Mentions: Spectra for the sampleswith xint = 0.16, 0.24, 0.36, 0.54, 0.64,and 0.84 are shown in Figure 5. 71Ga (spin quantum number I = 3/2, natural abundance39.6%) is a quadrupole nucleus; the interaction of its rather largequadrupole moment (Q = 10.7 × 10–30 m2) with the surrounding electric field gradient resultsin a central line that is perturbed by second-order effects. Theirshape can be simulated well with a single set of NMR parameters, namelyan isotropic chemical shift, δ, of 244(2) ppm, a quadrupolarcoupling constant, CQ, of 4.0(2) MHz,and an asymmetry parameter, ηQ, of 0.46(3). The spectrumof the sample with xint = 0.84, whichhas a slightly different line shape than those in the spectra of theother garnets (Figure 5), also has a NMR resonancewith the major component at δ = 244(2) ppm. The spectra forsamples with Ga3+ contents, xint ≥ 0.36, show the best signal to background ratios.

Bottom Line: The unit-cell parameter, a0, of the various garnets does not vary significantly as a function of Ga(3+) content, with a value of about 12.984(4) Å.Full chemical analyses for the solid solutions were obtained giving: Li7.08Ga0.06La2.93Zr2.02O12, Li6.50Ga0.15La2.96Zr2.05O12, Li6.48Ga0.23La2.93Zr2.04O12, Li5.93Ga0.36La2.94Zr2.01O12, Li5.38Ga0.53La2.96Zr1.99O12, Li4.82Ga0.60La2.96Zr2.00O12, and Li4.53Ga0.72La2.94Zr1.98O12.The NMR spectra are interpreted as indicating that Ga(3+) mainly occurs in a distorted 4-fold coordinated environment that probably corresponds to the general 96h crystallographic site of garnet.

View Article: PubMed Central - PubMed

Affiliation: Department of Materials Science and Physics, University of Salzburg , Hellbrunnerstrasse 34, A-5020 Salzburg, Austria.

ABSTRACT
Fast-conducting phase-pure cubic Ga-bearing Li7La3Zr2O12 was obtained using solid-state synthesis methods with 0.08 to 0.52 Ga(3+) pfu in the garnet. An upper limit of 0.72 Ga(3+) pfu in garnet was obtained, but the synthesis was accompanied by small amounts of La2Zr2O12 and LiGaO3. The synthetic products were characterized by X-ray powder diffraction, electron microprobe and SEM analyses, ICP-OES measurements, and (71)Ga MAS NMR spectroscopy. The unit-cell parameter, a0, of the various garnets does not vary significantly as a function of Ga(3+) content, with a value of about 12.984(4) Å. Full chemical analyses for the solid solutions were obtained giving: Li7.08Ga0.06La2.93Zr2.02O12, Li6.50Ga0.15La2.96Zr2.05O12, Li6.48Ga0.23La2.93Zr2.04O12, Li5.93Ga0.36La2.94Zr2.01O12, Li5.38Ga0.53La2.96Zr1.99O12, Li4.82Ga0.60La2.96Zr2.00O12, and Li4.53Ga0.72La2.94Zr1.98O12. The NMR spectra are interpreted as indicating that Ga(3+) mainly occurs in a distorted 4-fold coordinated environment that probably corresponds to the general 96h crystallographic site of garnet.

No MeSH data available.