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On Aliovalent Substitution on the Li Site in LiMPO4: an ­X-ray Diffraction Study of the Systems LiMPO4-M1.5PO4(= LixM1.5-x/2PO4; M = Ni, Co, Fe, Mn)

Clemens, Oliver and Haberkorn, Robert and Springborg, Michael and Beck, Horst Philipp (2014):
On Aliovalent Substitution on the Li Site in LiMPO4: an ­X-ray Diffraction Study of the Systems LiMPO4-M1.5PO4(= LixM1.5-x/2PO4; M = Ni, Co, Fe, Mn).
In: Zeitschrift für anorganische und allgemeine Chemie, 640 (1), WILEY-VCH Verlag GmbH & Co. KGaA, pp. 173-183, ISSN 00442313,
[Online-Edition: http://dx.doi.org/10.1002/zaac.201300376],
[Article]

Abstract

In this paper we report on the possibility of Li substitution by M2+ to various high degrees in LiMPO4 olivine-type compounds (M = Ni, Co, Fe, Mn), depending on the kind of transition metal M. The experimental studies were carried through by reacting stoichiometric amounts of LiMIIPO4 and MII1.5PO4 (= MII3(PO4)2) to form compounds of composition LixMII1.5–x/2PO4 (0 ≤ x ≤ 1). A complete solid solution over the whole range of x was found for M = Ni (together with a second order structural transition from orthorhombic to monoclinic for decreasing x), whereas far smaller degrees of dopability of the Li site were found for LiCoPO4 and LiFePO4 (up to compositions of approx. (Li0.8Co0.1)CoPO4 and approx. (Li0.9Fe0.05)FeO4. In addition, the nearly stoichiometric monoclinically distorted olivine-type compounds with compositions (Li0.42–0.47Co0.29–0.265)CoPO4 and (Li0.14–0.16Fe0.43–0.42)FePO4 could be identified and are described in this article.

Item Type: Article
Erschienen: 2014
Creators: Clemens, Oliver and Haberkorn, Robert and Springborg, Michael and Beck, Horst Philipp
Title: On Aliovalent Substitution on the Li Site in LiMPO4: an ­X-ray Diffraction Study of the Systems LiMPO4-M1.5PO4(= LixM1.5-x/2PO4; M = Ni, Co, Fe, Mn)
Language: English
Abstract:

In this paper we report on the possibility of Li substitution by M2+ to various high degrees in LiMPO4 olivine-type compounds (M = Ni, Co, Fe, Mn), depending on the kind of transition metal M. The experimental studies were carried through by reacting stoichiometric amounts of LiMIIPO4 and MII1.5PO4 (= MII3(PO4)2) to form compounds of composition LixMII1.5–x/2PO4 (0 ≤ x ≤ 1). A complete solid solution over the whole range of x was found for M = Ni (together with a second order structural transition from orthorhombic to monoclinic for decreasing x), whereas far smaller degrees of dopability of the Li site were found for LiCoPO4 and LiFePO4 (up to compositions of approx. (Li0.8Co0.1)CoPO4 and approx. (Li0.9Fe0.05)FeO4. In addition, the nearly stoichiometric monoclinically distorted olivine-type compounds with compositions (Li0.42–0.47Co0.29–0.265)CoPO4 and (Li0.14–0.16Fe0.43–0.42)FePO4 could be identified and are described in this article.

Journal or Publication Title: Zeitschrift für anorganische und allgemeine Chemie
Volume: 640
Number: 1
Publisher: WILEY-VCH Verlag GmbH & Co. KGaA
Uncontrolled Keywords: LiFePO4, LiMnPO4, LiCoPO4, LiNiPO4, Olivine-type compounds, Aliovalent substitution, Lithium, Phosphorus
Divisions: 11 Department of Materials and Earth Sciences > Material Science > Joint Research Laboratory Nanomaterials
11 Department of Materials and Earth Sciences > Material Science
11 Department of Materials and Earth Sciences
Date Deposited: 16 Feb 2015 13:25
Official URL: http://dx.doi.org/10.1002/zaac.201300376
Identification Number: doi:10.1002/zaac.201300376
Funders: Oliver Clemens thanks the Landesgraduiertenförderung Saarland for financial support.
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