Cu{sub 22}Bi{sub 12}S{sub 21}Cl{sub 16}-A mixed conductor with fast one-dimensional copper(I) ion transport
- Department of Chemistry and Food Chemistry, Dresden University of Technology, 01062 Dresden (Germany)
- Max Planck Institute for Solid State Research, Heisenbergstr. 1, 70569 Stuttgart (Germany)
Melting reactions of Cu, CuCl, S, and Bi{sub 2}S{sub 3} yield black, shiny needles of Cu{sub 22(1)}Bi{sub 12}S{sub 21(1)}Cl{sub 16(1)}. The compound decomposes peritectically at 649(5) K. Oxidation state +I of the copper atoms is supported by Cu-K-XANES. The compound crystallizes in the hexagonal space group P6/m with a=2116.7(7) pm and c=395.17(5) pm. Seven anions coordinate each of the two independent bismuth cations in the shape of mono-capped trigonal prisms. These polyhedra share edges and faces to form trigonal and hexagonal tubes running along [0 0 1]. The hexagonal tubes are centered by chloride ions, which are surrounded by disordered copper cations. The majority of copper cations are distributed over numerous sites between the tubes. The Joint Probability Density Function (JPDF) reveals a continuous pathway along [0 0 1]. The high mobility of the copper cations along [0 0 1] was demonstrated by impedance spectroscopy and DC polarization measurements on single crystals. The ionic conductivity at 450 K is about {sigma}{sub ion}=0.06 S cm{sup -1}, and the activation energy for Cu{sup +} ion conduction is E{sub a}=0.44 eV. The chemical diffusion coefficient of copper is in the order of D{sub cu}{sup {delta}=}10{sup 19} cm{sup -3} at 420 K. The electronic band gap (p-type conductor) was determined as E{sub g}=0.06 eV. At room temperature the thermal conductivity of a pressed pellet is about {kappa}=0.3 W K{sup -1} m{sup -1} and the Seebeck coefficient is S=43 {mu}V K{sup -1}. -- Graphical Abstract: Copper cations easily move through the rigid tubular crystal structure of Cu{sub 22}Bi{sub 12}S{sub 21}Cl{sub 16}. Display Omitted
- OSTI ID:
- 21504040
- Journal Information:
- Journal of Solid State Chemistry, Vol. 184, Issue 1; Other Information: DOI: 10.1016/j.jssc.2010.10.038; PII: S0022-4596(10)00495-0; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
Similar Records
The intergrowth structure of Ag{sub 1.2}Bi{sub 17.6}S{sub 23}Cl{sub 8} and its relation to the tubular structure of Bi{sub 6+} {sub {delta}} S{sub 6+3} {sub {delta}} Cl{sub 6-3} {sub {delta}} and the pavonite homologue Ag{sub 3} {sub x} Bi{sub 5-3} {sub x} S{sub 8-6} {sub x} Cl{sub 6} {sub x} {sub -1}
Mixed-Valent NaCu 4 Se 3: A Two-Dimensional Metal
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTROSCOPY
ANIONS
BISMUTH COMPOUNDS
BISMUTH SULFIDES
CATIONS
CHLORIDES
CHLORINE IONS
COPPER
COPPER CHLORIDES
COPPER COMPOUNDS
COPPER IONS
IONIC CONDUCTIVITY
MILLI EV RANGE
P-TYPE CONDUCTORS
SULFIDES
TEMPERATURE RANGE 0273-0400 K
TEMPERATURE RANGE 0400-1000 K
THERMAL CONDUCTIVITY
X-RAY SPECTROSCOPY
CHALCOGENIDES
CHARGED PARTICLES
CHLORINE COMPOUNDS
COPPER HALIDES
ELECTRIC CONDUCTIVITY
ELECTRICAL PROPERTIES
ELEMENTS
ENERGY RANGE
HALIDES
HALOGEN COMPOUNDS
IONS
MATERIALS
METALS
PHYSICAL PROPERTIES
SEMICONDUCTOR MATERIALS
SPECTROSCOPY
SULFUR COMPOUNDS
TEMPERATURE RANGE
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS