A type-II clathrate with a Li-Ge framework

作者：Boehme Bodo; Wei Kaya; Bobnar Matej; Prots Yurii; Burkhardt Ulrich; Baitinger Michael; Nolas George S; Grin Yuri

来源：Zeitschrift fur Kristallographie-Crystalline Materials, 2017, 232(7-9): 543-556.

DOI：10.1515/zkri-2017-2046

• framework substitution
• germanium
• intermetallic clathrate
• lithium
• solid state NMR

Na (16) Cs (8) Li x Ge (136-x) ( x approximate to 2.8, space group Fd (3) over barm) is the first intermetallic type-II clathrate with a lithiumsubstituted framework. The phase was obtained from the elements in sealed Ta ampoules by annealing at 650 degrees C for 5 days. Samples were investigated by synchrotron X-ray powder diffraction, solid-state NMR, microstructure and chemical analysis. The substitution of Ge by Li atoms causes a marked shrinking of the lattice parameter. Studies by Li-7 NMR confirmed the presence of Li in the clathrate phase and the Na-23 and Cs-133 NMR spectra consistently showed distinct changes as compared to the ternary Na (16) Cs-8 Ge-136. The SEDOR technique revealed a distance between Li and Cs atoms in agreement with the result of crystal structure refinement, indicating Li substitution at site 96g. The distinct Knight shift of all NMR signals implies metallic behaviour of the clathrate phase, measurements of the magnetic susceptibility indicate diamagnetic behaviour.

• 出版日期2017-7