Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-15 (D), 81377, München, Germany.
Angew Chem Int Ed Engl. 2016 Oct 17;55(43):13585-13588. doi: 10.1002/anie.201607074. Epub 2016 Sep 27.
The new phosphidosilicates Li SiP and LiSi P were synthesized by heating the elements at 1123 K and characterized by single-crystal X-ray diffraction. Li SiP (I4 /acd, Z=32, a=12.111(1) Å, c=18.658(2) Å) contains two interpenetrating diamond-like tetrahedral networks consisting of corner-sharing T2 supertetrahedra [(SiP ) ]. Sphalerite-like interpenetrating networks of uniquely bridged T4 and T5 supertetrahedra make up the complex structure of LiSi P (I4 /a, Z=100, a=18.4757(3) Å, c=35.0982(6) Å). The lithium ions are located in the open spaces between the supertetrahedra and coordinated by four to six phosphorus atoms. Temperature-dependent Li solid-state MAS NMR spectroscopic data indicate high mobility of the Li ions with low activation energies of 0.10 eV in Li SiP and 0.07 eV in LiSi P .
新的磷硅酸盐 LiSiP 和 LiSiP 是通过在 1123 K 下加热元素合成的，并通过单晶 X 射线衍射进行了表征。LiSiP（I4 /acd，Z=32，a=12.111（1）Å，c=18.658（2）Å）包含两个相互贯穿的金刚石状四面体网络，由顶角共享的 T2 超四面体组成[（SiP）]。闪锌矿状相互贯穿的 T4 和 T5 超四面体网络构成了 LiSiP（I4 /a，Z=100，a=18.4757（3）Å，c=35.0982（6）Å）的复杂结构。锂离子位于超四面体之间的开放空间中，并由四到六个磷原子配位。Li 固态 MAS NMR 光谱数据表明，Li 离子具有较高的迁移率，在 LiSiP 中的活化能低至 0.10 eV，在 LiSiP 中的活化能低至 0.07 eV。
