Bi{sub 1−x}Nb{sub x}O{sub 1.5+x} (x=0.0625, 0.12) fast ion conductors: Structures, stability and oxide ion migration pathways
- Department of Chemistry, Durham University, Science Site, South Road, Durham DH1 3LE (United Kingdom)
- Australian Nuclear Science and Technology Organisation, Lucas Heights 2234, NSW (Australia)
- Research School of Chemistry, Australian National University, Canberra, ACT (Australia)
- Institut Laue-Langevin, Grenoble (France)
A combined experimental and computational study of Bi{sub 1−x}Nb{sub x}O{sub 1.5+x} (x=0.0625 and 0.12) has been carried out using laboratory X-ray, neutron and electron diffraction, impedance measurements and ab-initio molecular dynamics. We demonstrate that Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625}, previously reported to adopt a cubic fluorite-type superstructure, can form two different polymorphs depending on the synthetic method: a metastable cubic phase is produced by quenching; while slower cooling yields a stable material with a tetragonal √2×√2×1 superstructure, which undergoes a reversible phase transition into the cubic form at ~680 °C on subsequent reheating. Neutron diffraction reveals that the tetragonal superstructure arises mainly from ordering in the oxygen sublattice, with Bi and Nb remaining disordered, although structured diffuse scattering observed in the electron diffraction patterns suggests a degree of short-range ordering. Both materials are oxide ion conductors. On thermal cycling, Bi{sub 0.88}Nb{sub 0.12}O{sub 1.62} exhibits a decrease in conductivity of approximately an order of magnitude due to partial transformation into the tetragonal phase, but still exhibits conductivity comparable to yttria-stabilised zirconia (YSZ). Ab-initio molecular dynamics simulations performed on Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625} show that oxide ion diffusion occurs by O{sup 2−} jumps between edge- and corner-sharing OM{sub 4} groups (M=Bi, Nb) via tetrahedral □M{sub 4} and octahedral □M{sub 6} vacancies. - Graphical abstract: Oxide ion migration in tetragonal Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625} occurs by O{sup 2−} jumps between edge- and corner-sharing OM{sub 4} groups (M=Bi, Nb) via tetrahedral M{sub 4} and octahedral M{sub 6} vacancies. - Highlights: • Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625} adopts a tetragonal √2×√2×1 fluorite superstructure. • Superstructure is due to ordering in the O-sublattice, with Bi/Nb disordered. • Bi{sub 0.9375}Nb{sub 0.0625}O{sub 1.5625} is a good oxide ion conductor. • O{sup 2−} jump between OM{sub 4} groups (M=Bi, Nb) via tetrahedral and octahedral vacancies.
- OSTI ID:
- 22475619
- Journal Information:
- Journal of Solid State Chemistry, Vol. 225; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
Similar Records
Structure and crystal chemistry of fluorite-related Bi{sub 38}Mo{sub 7}O{sub 78} from single crystal X-ray diffraction and ab initio calculations
Synthesis of anion-deficient layered perovskites, ACa[sub 2]Nb[sub 3-x]M[sub x]O[sub 10-x] (A = Rb, Cs; M = Al, Fe), exhibiting ion-exchange and intercalation. Evidence for the formation of layered brownmillerites, ACa[sub 2]Nb[sub 2]AlO[sub 9] (A = Cs, H)
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BISMUTH COMPOUNDS
COMPARATIVE EVALUATIONS
DIFFUSE SCATTERING
DIFFUSION
ELECTRON DIFFRACTION
IMPEDANCE
IONIC CONDUCTIVITY
MOLECULAR DYNAMICS METHOD
NEUTRON DIFFRACTION
NIOBIUM OXIDES
PHASE TRANSFORMATIONS
THERMAL CYCLING
VACANCIES
YTTRIUM OXIDES
ZIRCONIUM OXIDES