Fluorine conducting ceramics based on BiF3

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Abstract

The temperature dependence of the ionic conductivity of a ceramic sample of the Bi0.94Ba0.06F2.94 solid electrolyte was studied using impedance spectroscopy in the temperature range 293–473 K. The ceramics was obtained by solid-phase synthesis (873 K, 3 h) in a closed Cu ampoule and is a heterovalent solid solution of tysonite structure (space group) with lattice parameters a = 7.1482(8) and c = 7.3279(5) Å. The conductivity value at room temperature and its activation enthalpy are equal to σcer = 3 × 10–5 S/cm and DHs = 0.49 ± 0.05 eV, respectively. The ion-conducting properties of isostructural solid electrolytes Bi1–yBayF3–y and La1–yBayF3–y with similar values of ionic radii of matrix cations (1.17 and 1.16 Å for Bi3+ and La3+, respectively) are compared. The conductivity at 473 K of Bi0.94Ba0.06F2.94 ceramics exceeds the electrical conductivity of ceramics and La0.95Ba0.05F2.95 single crystals by 6 and 3.3 times, respectively.

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About the authors

N. I. Sorokin

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Author for correspondence.
Email: nsorokin1@yandex.ru
Russian Federation, Moscow

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Supplementary files

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2. Fig. 1. Impedance plot and equivalent electrical circuit for the electrochemical system Ag|Bi0.94Ba0.06F2.94|Ag ceramics at 294 K. The numbers at the shaded points indicate the frequency in kHz. The total resistance of the ceramic sample is Rcer = Rig + Rgb = 6.5×104 Ohm (Rig << Rcer).

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3. Fig. 2. Concentration dependence of intragranular conductivity of Bi1–yBayF3–y polycrystals: 1 – data from the conducted study, 2 – data from [7, 18], 3 – data from [19].

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4. Fig. 3. Temperature dependences of the anionic conductivity of fluoride ceramics Bi0.94Ba0.06F2.94 in coordinates lgσT, 103/T: 1, 2 – first sample, 3, 4 – second sample, 1, 3 – heating, 2, 4 – cooling.

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5. Fig. 4. Temperature dependences of the anionic conductivity of fluoride materials in the coordinates lgσ, 103/T: 1 – Bi0.94Ba0.06F2.94 ceramics (heating), 2 – BiF3 polycrystal [3], 3 – Bi1–yKyF3–2y polycrystal [20], 4 – Bi1–yPbyF3–y polycrystal [25], 5 – La0.95Ba0.05F2.95 ceramics [26, 27], 6 – La0.95Ba0.05F2.95 single crystal [28].

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