High anion conductivity in a ternary non-equilibrium phase of BaF 2 and CaF2 with mixed cations

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OriginalspracheEnglisch
Seiten (von - bis)3071-3081
Seitenumfang11
FachzeitschriftPhysical Chemistry Chemical Physics
Jahrgang11
Ausgabenummer17
PublikationsstatusVeröffentlicht - 19 März 2009

Abstract

A highly conductive ternary fluoride with mixed cations is prepared by joint high-energy ball milling of cubic BaF2 and CaF2 in the ratio 0.4:0.6. The sample produced at room temperature consists of a nanocrystalline, defect-rich mixed (Ba,Ca)F2 phase with retained cubic symmetry as well as of single-phase CaF2 particles. The anion conductivity of the mixed phase, which decomposes at higher temperature (770 K) into BaF2 and CaF2, exceeds that of single-phase nanocrystalline BaF2 by two and that of CaF2 by four orders of magnitude. In turn, these conductivities are each greater by about two orders than those of the respective microcrystalline counterparts. Structural features of the samples are characterized by X-ray diffraction, TEM and 19F MAS NMR spectroscopy. Static 19F NMR spectra confirm the unexpectedly high anion conductivity probed by impedance spectroscopy.

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High anion conductivity in a ternary non-equilibrium phase of BaF 2 and CaF2 with mixed cations. / Ruprecht, Benjamin; Wilkening, M.; Feldhoff, Armin et al.
in: Physical Chemistry Chemical Physics, Jahrgang 11, Nr. 17, 19.03.2009, S. 3071-3081.

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

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T1 - High anion conductivity in a ternary non-equilibrium phase of BaF 2 and CaF2 with mixed cations

AU - Ruprecht, Benjamin

AU - Wilkening, M.

AU - Feldhoff, Armin

AU - Steuernagel, S.

AU - Heitjans, Paul

PY - 2009/3/19

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N2 - A highly conductive ternary fluoride with mixed cations is prepared by joint high-energy ball milling of cubic BaF2 and CaF2 in the ratio 0.4:0.6. The sample produced at room temperature consists of a nanocrystalline, defect-rich mixed (Ba,Ca)F2 phase with retained cubic symmetry as well as of single-phase CaF2 particles. The anion conductivity of the mixed phase, which decomposes at higher temperature (770 K) into BaF2 and CaF2, exceeds that of single-phase nanocrystalline BaF2 by two and that of CaF2 by four orders of magnitude. In turn, these conductivities are each greater by about two orders than those of the respective microcrystalline counterparts. Structural features of the samples are characterized by X-ray diffraction, TEM and 19F MAS NMR spectroscopy. Static 19F NMR spectra confirm the unexpectedly high anion conductivity probed by impedance spectroscopy.

AB - A highly conductive ternary fluoride with mixed cations is prepared by joint high-energy ball milling of cubic BaF2 and CaF2 in the ratio 0.4:0.6. The sample produced at room temperature consists of a nanocrystalline, defect-rich mixed (Ba,Ca)F2 phase with retained cubic symmetry as well as of single-phase CaF2 particles. The anion conductivity of the mixed phase, which decomposes at higher temperature (770 K) into BaF2 and CaF2, exceeds that of single-phase nanocrystalline BaF2 by two and that of CaF2 by four orders of magnitude. In turn, these conductivities are each greater by about two orders than those of the respective microcrystalline counterparts. Structural features of the samples are characterized by X-ray diffraction, TEM and 19F MAS NMR spectroscopy. Static 19F NMR spectra confirm the unexpectedly high anion conductivity probed by impedance spectroscopy.

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