Premium
Li + Ion Conductors with Adamantane‐Type Nitridophosphate Anions β‐Li 10 P 4 N 10 and Li 13 P 4 N 10 X 3 with X =Cl, Br
Author(s) -
Bertschler EvaMaria,
Dietrich Christian,
Leichtweiß Thomas,
Janek Jürgen,
Schnick Wolfgang
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704305
Subject(s) - crystallography , octahedron , ion , chemistry , crystal structure , x ray photoelectron spectroscopy , space group , sphalerite , x ray crystallography , diffraction , mineralogy , nuclear magnetic resonance , physics , pyrite , organic chemistry , optics
β‐Li 10 P 4 N 10 and Li 13 P 4 N 10 X 3 with X =Cl, Br have been synthesized from mixtures of P 3 N 5 , Li 3 N, Li X , LiPN 2 , and Li 7 PN 4 at temperatures below 850 °C. β‐Li 10 P 4 N 10 is the low‐temperature polymorph of α‐Li 10 P 4 N 10 and crystallizes in the trigonal space group R 3. It is made up of non‐condensed [P 4 N 10 ] 10− T2 supertetrahedra, which are arranged in sphalerite‐analogous packing. Li 13 P 4 N 10 X 3 ( X =Cl, Br) crystallizes in the cubic space group F m 3 ‾ m . Both isomorphic compounds comprise adamantane‐type [P 4 N 10 ] 10− , Li + ions, and halides, which form octahedra. These octahedra build up a face‐centered cubic packing, whose tetrahedral voids are occupied by the [P 4 N 10 ] 10− ions. The crystal structures have been elucidated from X‐ray powder diffraction data and corroborated by EDX measurements, solid‐state NMR, and FTIR spectroscopy. Furthermore, we have examined the phase transition between α‐ and β‐Li 10 P 4 N 10 . To confirm the ionic character, the migration pathways of the Li + ions have been evaluated and the ion conductivity and its temperature dependence have been determined by impedance spectroscopy. XPS measurements have been carried out to analyze the stability with respect to Li metal.