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Thomas Rothenaigner , Arno Pfitzner* SbS SbS – Ag Li Ag Sb S – a compound in the quasi-binary system Li

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Li

2

Ag

7

Sb

3

S

9

– a compound in the quasi-binary system Li

3

SbS

3

Ag

3

SbS

3

Thomas Rothenaigner

[a]

, Arno Pfitzner*

[a]

[a] Institut für Anorganische Chemie Universität Regensburg

Universitätsstraße 31 93040 Regensburg, Germany

* Prof. Dr. A. Pfitzner

E-Mail: arno.pfitzner@chemie.uni-regensburg.de

Keywords: Crystal Structure, Ionic Conductor, Lithium Silver Antimony Sulfide

In literature there are many compounds known with the composition M3SbS3 (M=Ag[1], Cu[2,3], Li[4], Na[5], K[6] , Rb[6], Cs[6]). We investigated the quasi-binary section Li3SbS3 – Ag3SbS3 for new quaternary materials. Li2Ag7Sb3S9 has been synthesized by high temperature reaction of Li2S, Ag2S and Sb2S3. The crystal structure of Li2Ag7Sb3S9 was determined by single-crystal X-ray diffraction. The title compound crystallizes in the orthorhombic space group Pnma (No. 62) with a = 24.411(3) Å, b = 10.620(1) Å, c = 6.939(1) Å, V = 1798.9(5) Å3, and Z = 4.

The anionic substructure of Li2Ag7Sb3S9 consists of trigonal- pyramidal SbS3, tetrahedral LiS4 and trigonal-planar AgS3 units.

(Figure 1).

Thermal analysis revealed a reversible phase transition at 235°C and a melting point of 480°C.

The compound was further characterized by Raman spectroscopy.

The Sb-S vibrations at 320 cm-1 and 287 cm-1 are in good agreement with data in literature [7].

Impedance spectroscopy shows an ionic conductivity of 10-7 S/cm at room temperature and 10-3 S/cm at 300°C.

Figure 1. Section of the crystal structure of Li2Ag7Sb3S9. Lithium is located in the distorted tetrahedra.

[1] F. Laufek, J. Sejkora, M. Dusek, J. Geosci., 2010, 23, 21-26.

[2] E. Makovicky, T. Balic-Zunic, Can. Mineral., 1995, 33, 655- 663.

[3] A. Pfitzner, Z. Anorg. Allg. Chem., 1994, 620, 1992-1997.

[4] S. Huber, C. Preitschaft, R. Weihrich, A. Pfitzner, Z. Anorg.

Allg. Chem., 2012, 638, 2542-2548.

[5] C. Pompe, A. Pfitzner, Z. Anorg. Allg. Chem., 2013, 639, 296- 300.

[6] L. Schindler, M. Schwarz, C. Röhr, Z. Naturforsch. B., 2013, 68(12), 1295-1309.

[7] A. Pfitzner, Chem. Eur. J., 1997, 3, 2032-2038.

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