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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >On Aliovalent Substitution on the Li Site in LiMPO_4: an X-ray Diffraction Study of the Systems LiMPO_4-M_(1.5)PO_4 (= LixM_(1.5-x/2)PO_4; M = Ni, Co, Fe, Mn)
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On Aliovalent Substitution on the Li Site in LiMPO_4: an X-ray Diffraction Study of the Systems LiMPO_4-M_(1.5)PO_4 (= LixM_(1.5-x/2)PO_4; M = Ni, Co, Fe, Mn)

机译：关于LiMPO_4的Li位上的异价取代：系统LiMPO_4-M_（1.5）PO_4（= LixM_（1.5-x / 2）PO_4; M = Ni，Co，Fe，Mn）的X射线衍射研究

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摘要

In this paper we report on the possibility of Li substitution by M~(2+) to various high degrees in LiMPO_4 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~(II)PO_4 and M~(II)_(1.5)PO_4 (= M~(II)_3(PO_4)_2) to form compounds of composition LixM~(II)_(1.5-x/2)PO_4 (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 LiCoPO_4 and LiFePO_4 (up to compositions of approx. (Li_(0.8)Co_(0.1))CoPO_4 and approx. (Li_(0.9)Fe_(0.05))FeO_4. In addition, the nearly stoichiometric monoclinically distorted olivine-type compounds with compositions (Li_(0.42-0.47)Co_(0.29-0.265))CoPO_4 and (Li_(0.14-0.16)Fe_(0.43-0.42))FePO_4 could be identified and are described in this article.
机译：本文根据过渡金属M的种类，报道了LiMPO_4橄榄石型化合物（M = Ni，Co，Fe，Mn）中M〜（2+）可以不同程度地取代Li的可能性。通过使化学计量的LiM〜（II）PO_4和M〜（II）_（1.5）PO_4（= M〜（II）_3（PO_4）_2）反应形成组成为LixM〜（II）的化合物来进行实验研究_（1.5-x / 2）PO_4（0≤x≤1）。对于M = Ni，发现在x的整个范围内有完整的固溶体（同时伴随着从正交晶向单斜晶的二阶结构转变，从而使x减小），而对于LiCoPO_4和LiFePO_4，发现Li位的掺杂度要小得多（最多约（Li_（0.8）Co_（0.1））CoPO_4和约（Li_（0.9）Fe_（0.05））FeO_4的组成。此外，几乎化学计量的单临床畸变橄榄石型化合物的组成为（Li_（0.42 -0.47）Co_（0.29-0.265）CoPO_4和（Li_（0.14-0.16）Fe_（0.43-0.42））FePO_4可以被识别并在本文中进行描述。

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