Mechanosynthesis of the Fast Fluoride Ion Conductor Ba1–xLaxF2+x: From the Fluorite to the Tysonite Structure

A. Düvel; J. Bednarcik; V. Šepelák; P. Heitjans

doi:10.1021/jp410018t

New fluoride ion conductor, K x Bi 1−x F 3−2x (.02≤ x ≤.12), with the tysonite structure

Solid State Ionics ◽

10.1016/0167-2738(81)90334-9 ◽

1981 ◽

Vol 5 ◽

pp. 633-635 ◽

Cited By ~ 22

Author(s):

M.W. Shafer ◽

G.V. Chandrashekhar ◽

R.A. Figat

Keyword(s):

Fluoride Ion ◽

Ion Conductor ◽

Tysonite Structure

High fluoride-ion conductivity and fluoride-ion conductor−insulator transition in fluorinated hexagonal boron nitride

Materials Today Physics ◽

10.1016/j.mtphys.2021.100523 ◽

2021 ◽

Vol 21 ◽

pp. 100523

Author(s):

Tsuyoshi Takami ◽

Takashi Saito ◽

Takashi Kamiyama ◽

Katsumi Kawahara ◽

Toshiharu Fukunaga ◽

...

Keyword(s):

Boron Nitride ◽

Hexagonal Boron Nitride ◽

Insulator Transition ◽

Ion Conductivity ◽

Fluoride Ion ◽

Ion Conductor ◽

High Fluoride

Kinetics of Phase Transitions in Superionic Pbsnf4 Versus Temperature

MRS Proceedings ◽

10.1557/proc-398-525 ◽

1995 ◽

Vol 398 ◽

Cited By ~ 2

Author(s):

Georges Denes ◽

M. Cecilia Madamba ◽

Galina Milova

Keyword(s):

Phase Transitions ◽

Chemical Sensors ◽

Fluoride Ion ◽

Prolonged Heating ◽

Kinetics Of Phase Transitions ◽

Ion Conductor ◽

The Stability ◽

Short Time ◽

Kinetics Of ◽

Time Evaluation

ABSTRACTPbSnF4 is the highest performance fluoride ion conductor known to date and is starting to be used for the fabrication of chemical sensors. Although several phase transitions have been reported, with conflicting results from different groups, the exact sequence of phase transitions versus temperature and the kinetics of the phase transformations remain unclear. We have prepared the three phases that can be stabilized at ambient temperature, i.e. o-, α- and β-PbSnF4, and studied the stability of each phase versus temperature. It appears that some of the phases transform very slowly to another under prolonged heating at constant temperature. This is very important since the conductivity is not necessarily the same for each phase, and therefore, a phase transition taking place slowly in the PbSnF4 used for the fabrication of a device, might not be detectable by a short time evaluation but, it could well alter its properties after prolonged use.

Mechanochemical synthesis and order–disorder phase transition in fluoride ion conductor RbPbF3

Solid State Ionics ◽

10.1016/j.ssi.2008.04.022 ◽

2008 ◽

Vol 179 (17-18) ◽

pp. 605-610 ◽

Cited By ~ 12

Author(s):

Y YAMANE ◽

K YAMADA ◽

K INOUE

Keyword(s):

Phase Transition ◽

Mechanochemical Synthesis ◽

Fluoride Ion ◽

Ion Conductor ◽

Disorder Phase Transition

Structural phase transition of the two-dimensional fluoride ion conductor KSn2F5 studied by X-ray diffraction

Solid State Ionics ◽

10.1016/j.ssi.2003.09.004 ◽

2004 ◽

Vol 167 (3-4) ◽

pp. 301-307 ◽

Cited By ~ 14

Author(s):

K Yamada

Keyword(s):

Phase Transition ◽

Structural Phase Transition ◽

Structural Phase ◽

Fluoride Ion ◽

Two Dimensional ◽

X Ray Diffraction ◽

Ion Conductor ◽

X Ray

Effect of Preparation and Impurities on The Size and Shape of The Crystallites and on The Crystal Symmetry of Superionic PbSnF4

MRS Proceedings ◽

10.1557/proc-580-171 ◽

1999 ◽

Vol 580 ◽

Cited By ~ 2

Author(s):

Georges Dénès ◽

M. Cecilia Madamba

Keyword(s):

Local Structure ◽

Strong Influence ◽

Oxygen Sensor ◽

Fluoride Ion ◽

Crystal Shape ◽

Oriented Sample ◽

Ion Conductor ◽

Preferred Direction ◽

Polycrystalline Form ◽

Crystalline Symmetry

AbstractThe highest performance fluoride ion conductor, PbSnF4, has been applied for the fabrication of an ambient temperature amperometric oxygen sensor, where it is used in the polycrystalline form. However, the structure of this material is highly anisotropic, thus one could expect polycrystalline samples to give a performance strongly dependent on crystallite direction. We have shown that the tin electronic structure has a very strong influence on the local structure, which determines the preferred direction of crystal growth, which is itself responsible for the crystal shape. This, in turn, determines the direction of preferred orientation, which can dramatically alter the properties relative to a randomly oriented sample. The effect of minor impurities on the size of the crystallites and on the crystalline symmetry has been studied.

Neutron diffraction stufy of the high-fluoride-ion conductor, PbSnF4, prepared under an HF atmosphere

Solid State Ionics ◽

10.1016/0167-2738(94)90319-0 ◽

1994 ◽

Vol 70-71 ◽

pp. 253-258 ◽

Cited By ~ 14

Author(s):

R KANNO ◽

K OHNO ◽

H IZUMI ◽

Y KAWAMOTO ◽

T KAMIYAMA ◽

...

Keyword(s):

Neutron Diffraction ◽

Fluoride Ion ◽

Ion Conductor ◽

High Fluoride

Ionic Conductivity of the new Fluoride-Ion Conductor Casn2F6

MRS Proceedings ◽

10.1557/proc-756-ee3.5 ◽

2002 ◽

Vol 756 ◽

Author(s):

Michael F. Bell ◽

Georges DéNés ◽

Zhimeng Zhu

Keyword(s):

Solid Solution ◽

Complex Impedance ◽

Crystalline Material ◽

Mixed Conductor ◽

Impedance Method ◽

Fluoride Ion ◽

Ion Conductor ◽

Covalently Bonded ◽

Fluorite Type ◽

First Time

ABSTRACTMetastable CaSn2F6 has been prepared for the first time and characterized. It is a well crystalline material that leaches SnF2 in water to give the microcrystalline fluorite-type Ca1-xSnxF2 solid solution. In both materials, tin(II) is covalently bonded to fluorine, and thus carries a stereoactive non-bonding electronic pair. The electrical conductivity of CaSn2F6 was measured by the complex impedance method. The CaSn2F6 material was found to be a mixed conductor (τi = 0.50), with a F- conductivity a little below that of α-SnF2. On heating to 250°C, it decomposes irreversibly to give SnF2 and probably amorphous CaF2 (undetected).

Two dimensional fluoride ion conductor RbSn$_\mathsf{2}$F$_\mathsf{5}$ studied by impedance spectroscopy and $^\mathsf{19}$F, $^\mathsf{119}$Sn, and $^\mathsf{87}$Rb NMR

The European Physical Journal B ◽

10.1140/epjb/e2004-00255-1 ◽

2004 ◽

Vol 40 (2) ◽

pp. 167-176 ◽

Cited By ~ 16

Author(s):

K. Yamada ◽

M. M. Ahmad ◽

Y. Ogiso ◽

T. Okuda ◽

J. Chikami ◽

...

Keyword(s):

Impedance Spectroscopy ◽

Fluoride Ion ◽

Two Dimensional ◽

Ion Conductor

Studying Ionic Conductivity with Diffraction Techniques an Application to laF3

MRS Proceedings ◽

10.1557/proc-135-227 ◽

1988 ◽

Vol 135 ◽

Author(s):

Andreas Belzner ◽

Heinz Schulz

Keyword(s):

Activation Energy ◽

Ionic Conductivity ◽

Nearest Neighbor ◽

Fluoride Ion ◽

Static Disorder ◽

Ion Conductor ◽

3 Dimensional ◽

Thermal Vibrations ◽

Temperature Factors

AbstractThe LaF3-structure has been reinvestigated using diffraction data measured with twinned crystals.LaF3 is fluoride ion conductor with essentially 3-dimensional conductivity. The conduction perpendicular to the c-axis is shown to occur on paths which include all three sets of fluorine positions in the structure and which connect symmetrically non-equivalent nearest neighbor positions only. This is confirmed by determination of anharmonic temperature factors. The temperature dependence of the harmonic thermal parameters indicates that thermal vibrations are described rather than static disorder. The magnitude of the temperature factors of fluorine is consistent with an intrinsic activation energy of 0.8 eV for fluorine conduction.