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The solubility and site preference of Fe(3+) in Li7-3x Fe x La3Zr2O12 garnets.

Rettenwander D, Geiger CA, Tribus M, Tropper P, Wagner R, Tippelt G, Lottermoser W, Amthauer G - J Solid State Chem (2015)

Bottom Line: The lattice parameter, a 0, for all solid-solution garnets is similar with a value of a 0≈12.98 Å regardless of the amount of Fe(3+). (57)Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO3 in syntheses with Fe(3+) contents greater than 0.16 Fe(3+) pfu.The (57)Fe Mössbauer spectrum of cubic Li6.54Fe0.12La3.01Zr1.98O12 garnet indicates that most Fe(3+) occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet.Fe(3+) in smaller amounts occurs at a general 96h site, which is only present for certain Li-oxide garnets, and in Li6.54Fe0.12La3.01Zr1.98O12 this Fe(3+) has a distorted 4-fold coordination.

View Article: PubMed Central - PubMed

Affiliation: Department of Materials Research and Physics, University of Salzburg, 5020 Salzburg, Austria.

ABSTRACT

A series of Fe(3+)-bearing Li7La3Zr2O12 (LLZO) garnets was synthesized using solid-state synthesis methods. The synthetic products were characterized compositionally using electron microprobe analysis and inductively coupled plasma optical emission spectroscopy (ICP-OES) and structurally using X-ray powder diffraction and (57)Fe Mössbauer spectroscopy. A maximum of about 0.25 Fe(3+) pfu could be incorporated in Li7-3x Fe x La3Zr2O12 garnet solid solutions. At Fe(3+) concentrations lower than about 0.16 pfu, both tetragonal and cubic garnets were obtained in the synthesis experiments. X-ray powder diffraction analysis showed only a garnet phase for syntheses with starting materials having intended Fe(3+) contents lower than 0.52 Fe(3+) pfu. Back-scattered electron images made with an electron microprobe also showed no phase other than garnet for these compositions. The lattice parameter, a 0, for all solid-solution garnets is similar with a value of a 0≈12.98 Å regardless of the amount of Fe(3+). (57)Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO3 in syntheses with Fe(3+) contents greater than 0.16 Fe(3+) pfu. The composition of different phase pure Li7-3x Fe x La3Zr2O12 garnets, as determined by electron microprobe (Fe, La, Zr) and ICP-OES (Li) measurements, give Li6.89Fe0.03La3.05Zr2.01O12, Li6.66Fe0.06La3.06Zr2.01O12, Li6.54Fe0.12La3.01Zr1.98O12, and Li6.19Fe0.19La3.02Zr2.04O12. The (57)Fe Mössbauer spectrum of cubic Li6.54Fe0.12La3.01Zr1.98O12 garnet indicates that most Fe(3+) occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet. Fe(3+) in smaller amounts occurs at a general 96h site, which is only present for certain Li-oxide garnets, and in Li6.54Fe0.12La3.01Zr1.98O12 this Fe(3+) has a distorted 4-fold coordination.

No MeSH data available.


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Lattice parameter, a0, of Li7−3xFexLa3Zr2O12 with xint=0.04–0.72 and the various phases (%) for the different syntheses as determined by XRPD as a function of the intended mole fraction xint of Fe in LLZO garnet
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f0015: Lattice parameter, a0, of Li7−3xFexLa3Zr2O12 with xint=0.04–0.72 and the various phases (%) for the different syntheses as determined by XRPD as a function of the intended mole fraction xint of Fe in LLZO garnet


The solubility and site preference of Fe(3+) in Li7-3x Fe x La3Zr2O12 garnets.

Rettenwander D, Geiger CA, Tribus M, Tropper P, Wagner R, Tippelt G, Lottermoser W, Amthauer G - J Solid State Chem (2015)

Lattice parameter, a0, of Li7−3xFexLa3Zr2O12 with xint=0.04–0.72 and the various phases (%) for the different syntheses as determined by XRPD as a function of the intended mole fraction xint of Fe in LLZO garnet
© Copyright Policy - CC BY-NC-ND
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4554257&req=5

f0015: Lattice parameter, a0, of Li7−3xFexLa3Zr2O12 with xint=0.04–0.72 and the various phases (%) for the different syntheses as determined by XRPD as a function of the intended mole fraction xint of Fe in LLZO garnet
Bottom Line: The lattice parameter, a 0, for all solid-solution garnets is similar with a value of a 0≈12.98 Å regardless of the amount of Fe(3+). (57)Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO3 in syntheses with Fe(3+) contents greater than 0.16 Fe(3+) pfu.The (57)Fe Mössbauer spectrum of cubic Li6.54Fe0.12La3.01Zr1.98O12 garnet indicates that most Fe(3+) occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet.Fe(3+) in smaller amounts occurs at a general 96h site, which is only present for certain Li-oxide garnets, and in Li6.54Fe0.12La3.01Zr1.98O12 this Fe(3+) has a distorted 4-fold coordination.

View Article: PubMed Central - PubMed

Affiliation: Department of Materials Research and Physics, University of Salzburg, 5020 Salzburg, Austria.

ABSTRACT

A series of Fe(3+)-bearing Li7La3Zr2O12 (LLZO) garnets was synthesized using solid-state synthesis methods. The synthetic products were characterized compositionally using electron microprobe analysis and inductively coupled plasma optical emission spectroscopy (ICP-OES) and structurally using X-ray powder diffraction and (57)Fe Mössbauer spectroscopy. A maximum of about 0.25 Fe(3+) pfu could be incorporated in Li7-3x Fe x La3Zr2O12 garnet solid solutions. At Fe(3+) concentrations lower than about 0.16 pfu, both tetragonal and cubic garnets were obtained in the synthesis experiments. X-ray powder diffraction analysis showed only a garnet phase for syntheses with starting materials having intended Fe(3+) contents lower than 0.52 Fe(3+) pfu. Back-scattered electron images made with an electron microprobe also showed no phase other than garnet for these compositions. The lattice parameter, a 0, for all solid-solution garnets is similar with a value of a 0≈12.98 Å regardless of the amount of Fe(3+). (57)Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO3 in syntheses with Fe(3+) contents greater than 0.16 Fe(3+) pfu. The composition of different phase pure Li7-3x Fe x La3Zr2O12 garnets, as determined by electron microprobe (Fe, La, Zr) and ICP-OES (Li) measurements, give Li6.89Fe0.03La3.05Zr2.01O12, Li6.66Fe0.06La3.06Zr2.01O12, Li6.54Fe0.12La3.01Zr1.98O12, and Li6.19Fe0.19La3.02Zr2.04O12. The (57)Fe Mössbauer spectrum of cubic Li6.54Fe0.12La3.01Zr1.98O12 garnet indicates that most Fe(3+) occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet. Fe(3+) in smaller amounts occurs at a general 96h site, which is only present for certain Li-oxide garnets, and in Li6.54Fe0.12La3.01Zr1.98O12 this Fe(3+) has a distorted 4-fold coordination.

No MeSH data available.


Related in: MedlinePlus