Synthesis of nano-sized solid electrolyte Pr1–ySryF3–y and the effect of heat treatment on the ionic conductivity of fluoride nanoceramics

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Abstract

Solid electrolyte nanoceramics Pr1–ySryF3–y (y = 0.03, sp. gr. P3c1) were obtained by high-energy grinding of melt-grown crystals followed by cold pressing. The phase composition, microstructure, morphology, and electrical properties of nanoceramics were studied using X-ray diffraction analysis, electron microscopy and impedance spectroscopy. The room temperature conductivity of the synthesized Pr0.97Sr0.03F2.97 nanoceramics (σcer = 1.7 × 10–7 S/cm) is significantly lower than the conductivity of the original single crystal (σcrys = 4.0 × 10–4 S/cm), which is due to its low (about ~74% of the theoretical value) density. Heat treatment of nanoceramics at 823 K in vacuum leads to a 3-fold increase in the value of σcer, and annealing at 1273 K in a fluorinating atmosphere results in further increase in conductivity (σcer = 4.3 × 10–5 S/cm) due to the process of collective recrystallization and significant increase the density of ceramics up to 90%. The mechanical grinding technique and subsequent heat treatment of Pr1–ySryF3–y nanopowder makes it possible to processing single-phase highly conductive ceramics. The proposed method for the synthesis of ceramic fluoride nanomaterials as a technological form of solid electrolytes is a promising direction for further developments in the field of creating fluorine-ion current sources and fluorine gas sensors.

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About the authors

N. I. Sorokin

NRC “Kurchatov Institute”

Author for correspondence.
Email: nsorokin1@yandex.ru

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics

Russian Federation, Moscow

N. A. Arkharova

NRC “Kurchatov Institute”

Email: nsorokin1@yandex.ru

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics

Russian Federation, Moscow

D. N. Karimov

NRC “Kurchatov Institute”

Email: dnkarimov@gmail.com

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics

Russian Federation, Moscow

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Supplementary files

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2. Fig. 1. Section of the diagram of the SrF2–PrF3 system [29] (a). Transmission spectrum of Pr1–ySryF3–y crystals (y = 0.05 according to the batch composition), sample thickness 2 mm (b). The positions of the bands associated with the presence of Nd3+ ions are marked with the sign *. The inset shows the appearance of Pr0.97Sr0.03F2.97 crystal blocks obtained from the melt.

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3. Fig. 2. Diffraction patterns of the Pr1–ySryF3–y solid solution: 1 – directional crystallization of the melt, 2 – MD method, duration τ = 1 h, 3 – MD method, τ = 4 h, 4 – MD method, τ = 4 h and annealing at T = 1273 K, τ = 2 h. Shown are the calculated positions of the Bragg reflections for space group P3c1 with parameters a = 7.0802(1) and c = 7.2457(3) Å.

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4. Fig. 3. SEM images of Pr0.97Sr0.03F2.97 particles after MD for τ = 1 (a) and 4 h (b).

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5. Fig. 4. External appearance of a polycrystalline sample (a) and SEM image of the surface areas of ceramics obtained from Pr0.97Sr0.03F2.97 particles after τ = 1 (b) and = 4 h (c) of milling.

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6. Fig. 5. Impedance hodographs Z*(ω) for the initial (a) and annealed at 1273 K for 2 h (b) Pr0.97Sr0.03F2.97 ceramics with Ag electrodes at a temperature of 297 ± 1 K. The inset to Fig. 5a shows the equivalent electrical circuit, the numbers near the curves indicate the frequency in kHz. Resistance values: a – Rcer = 1.6 × 107 Ohm (extrapolation), b – Rcer = 7.5 × 104 Ohm, Rig = 8 × 103 Ohm.

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7. Fig. 6. SEM images of the surface of Pr0.97Sr0.03F2.97 ceramics obtained from particles by the MD method for τ = 1 (a), τ = 4 h (b) and annealed at 1273 K for 2 h, and the corresponding histograms of the distribution of crystalline grains by size.

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