The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets

A series of Fe3+-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 p...

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Main Authors:	Rettenwander, D., Geiger, C.A., Tribus, M., Tropper, P., Wagner, R., Tippelt, G., Lottermoser, W., Amthauer, G.
Format:	Online
Language:	English
Published:	Academic Press 2015
Online Access:	https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4554257/

id	pubmed-4554257
recordtype	oai_dc
spelling	pubmed-45542572015-10-01 The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets Rettenwander, D. Geiger, C.A. Tribus, M. Tropper, P. Wagner, R. Tippelt, G. Lottermoser, W. Amthauer, G. Article A series of Fe3+-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 57Fe Mössbauer spectroscopy. A maximum of about 0.25 Fe3+ pfu could be incorporated in Li7−3xFexLa3Zr2O12 garnet solid solutions. At Fe3+ 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 Fe3+ contents lower than 0.52 Fe3+ pfu. Back-scattered electron images made with an electron microprobe also showed no phase other than garnet for these compositions. The lattice parameter, a0, for all solid-solution garnets is similar with a value of a0≈12.98 Å regardless of the amount of Fe3+. 57Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO3 in syntheses with Fe3+ contents greater than 0.16 Fe3+ pfu. The composition of different phase pure Li7−3xFexLa3Zr2O12 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 57Fe Mössbauer spectrum of cubic Li6.54Fe0.12La3.01Zr1.98O12 garnet indicates that most Fe3+ occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet. Fe3+ 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 Fe3+ has a distorted 4-fold coordination. Academic Press 2015-10 /pmc/articles/PMC4554257/ /pubmed/26435549 http://dx.doi.org/10.1016/j.jssc.2015.01.016 Text en © 2015 The Authors http://creativecommons.org/licenses/by-nc-nd/4.0/ This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
repository_type	Open Access Journal
institution_category	Foreign Institution
institution	US National Center for Biotechnology Information
building	NCBI PubMed
collection	Online Access
language	English
format	Online
author	Rettenwander, D. Geiger, C.A. Tribus, M. Tropper, P. Wagner, R. Tippelt, G. Lottermoser, W. Amthauer, G.
spellingShingle	Rettenwander, D. Geiger, C.A. Tribus, M. Tropper, P. Wagner, R. Tippelt, G. Lottermoser, W. Amthauer, G. The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets
author_facet	Rettenwander, D. Geiger, C.A. Tribus, M. Tropper, P. Wagner, R. Tippelt, G. Lottermoser, W. Amthauer, G.
author_sort	Rettenwander, D.
title	The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets
title_short	The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets
title_full	The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets
title_fullStr	The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets
title_full_unstemmed	The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets
title_sort	solubility and site preference of fe3+ in li7−3xfexla3zr2o12 garnets
description	A series of Fe3+-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 57Fe Mössbauer spectroscopy. A maximum of about 0.25 Fe3+ pfu could be incorporated in Li7−3xFexLa3Zr2O12 garnet solid solutions. At Fe3+ 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 Fe3+ contents lower than 0.52 Fe3+ pfu. Back-scattered electron images made with an electron microprobe also showed no phase other than garnet for these compositions. The lattice parameter, a0, for all solid-solution garnets is similar with a value of a0≈12.98 Å regardless of the amount of Fe3+. 57Fe Mössbauer spectroscopic measurements indicate the presence of poorly- or nano-crystalline FeLaO3 in syntheses with Fe3+ contents greater than 0.16 Fe3+ pfu. The composition of different phase pure Li7−3xFexLa3Zr2O12 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 57Fe Mössbauer spectrum of cubic Li6.54Fe0.12La3.01Zr1.98O12 garnet indicates that most Fe3+ occurs at the special crystallographic 24d position, which is the standard tetrahedrally coordinated site in garnet. Fe3+ 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 Fe3+ has a distorted 4-fold coordination.
publisher	Academic Press
publishDate	2015
url	https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4554257/
_version_	1613470786526380032

The solubility and site preference of Fe3+ in Li7−3xFexLa3Zr2O12 garnets

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