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)
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)
复制标题
LiMPO4 中 Li 位点上的异价取代：LiMPO4–M1.5PO4 体系的 X 射线衍射研究（= LixM1.5–x/2PO4；M = Ni、Co、Fe、Mn）
DOI：
10.1002/zaac.201300376
复制
发表时间：
2014
期刊：
影响因子：
--
通讯作者：
H. Beck
中科院分区：
文献类型：
--
作者：
O. Clemens;R. Haberkorn;M. Springborg;H. Beck
本文报道了在LiMPO_4橄榄石型化合物（M = Ni，Co，Fe，Mn）中，M ~（2+）对Li进行不同程度取代的可能性，这取决于过渡金属M的种类。通过化学计量量的LiMIIPO 4和MII 1.5PO 4（= MII 3（PO 4）2）反应以形成组成为LixMII 1.5-x/2 PO 4（0 ≤ x ≤ 1）的化合物来进行实验研究。对于M = Ni，在整个x范围内发现了完全的固溶体（随着x的减小，从斜方晶系到单斜晶系的二级结构转变），而对于LiCoPO 4和LiFePO 4，发现Li位点的掺杂程度小得多（高达约100 μ m的组成）。（Li0.8Co0.1）CoPO 4和约（Li0.9Fe0.05）FeO 4。此外，还发现了（Li 0.42 - 0.47Co 0.29 -0.265）CoPO 4和（Li 0.14 - 0.16Fe 0.43 -0.42）FePO 4两种近化学计量的单斜晶系畸变橄榄石型化合物。
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.