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). Issue 1 (15th October 2013)

• Record Type: Journal Article
• Authors: Clemens, Oliver; Haberkorn, Robert; Springborg, Michael; Beck, Horst Philipp
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 640:Issue 1(2014)
• Page Start: 173
• Page End: 183
• Publication Date: 2013-10-15
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201300376
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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 LiM^IIPO₄ and M^II_1.5PO₄ (= M^II₃(PO₄)₂) to form compounds of composition Li<italic>_x</italic>M^II_{1.5–<italic>x</italic>/2}PO₄ (0 ≤ <italic>x</italic> ≤ 1). A complete solid solution over the whole range of <italic>x</italic> was found for M = Ni (together with a second order structural transition from orthorhombic to monoclinic for decreasing <italic>x</italic>), whereas far smaller degrees of dopability of the Li site were found for LiCoPO₄ and LiFePO₄ (up to compositions of approx. (Li_0.8Co_0.1)CoPO₄ and approx. (Li_0.9Fe_0.05)FeO₄. In addition, the nearly stoichiometric monoclinically distorted olivine‐type compounds with compositions (Li_0.42–0.47Co_0.29–0.265)CoPO₄ and (Li_0.14–0.16Fe_0.43–0.42)FePO₄ could be identified and are described in this article.</p> </abstract>