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) |
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| Authors: | Oliver Clemens Robert Haberkorn Michael Springborg Horst Philipp Beck |
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| Institution: | 1. Universit?t des Saarlandes, Institut für Anorganische und Analytische Chemie und Radiochemie, Am Markt, Zeile 5, 66125 Saarbrücken, Germany;2. Present address: TU Darmstadt, Joint Research Laboratory Nanomaterials, Petersenstra?e 32, 64287 Darmstadt, Germany, and KIT, Institut für Nanotechnologie, Hermann‐von‐Helmholtz‐Platz 1, 76344 Eggenstein‐Leopoldshafen, Germany;3. Universit?t des Saarlandes, Anorganische Festk?rperchemie, Am Markt, Zeile 3, 66125 Saarbrücken, Germany;4. Universit?t des Saarlandes, Physikalische und Theoretische Chemie, Campus B2 2, 66123 Saarbrücken, Germany |
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| 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. |
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| Keywords: | LiFePO4 LiMnPO4 LiCoPO4 LiNiPO4 Olivine‐type compounds Aliovalent substitution Lithium Phosphorus |
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