High-entropy columbites: structure, optical and electrical properties

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Abstract

A high-entropy composition (Mg0.2Zn0.2Ni0.2Co0.2Mn0.2)Nb2O6 with a columbite structure and its Ti-substituted composition (5%) were synthesized. The synthesis was carried out using a modified method of combustion solutions followed by high-temperature sintering. X-ray analysis and scanning electron microscopy were used for characterization of the ceramics. According to diffuse reflectance spectra, the band gap of direct electronic transitions was calculated (Egdir ≈ 2.98–3.05 eV). Solid solutions are characterized predominantly by electronic conductivity. Substitution of niobium cations with titanium leads to an increase in conductivity by 1.2 orders of magnitude in the temperature range 160–750°C.

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About the authors

M. S. Koroleva

Institute of Chemistry FRC Komi SC UB RAS

Email: marikorolevas@gmail.com
Russian Federation, Syktyvkar

V. S. Maksimov

Institute of Chemistry FRC Komi SC UB RAS; Pitirim Sorokin Syktyvkar State University

Author for correspondence.
Email: marikorolevas@gmail.com
Russian Federation, Syktyvkar; Syktyvkar

D. A. Korolev

ITMO University

Email: marikorolevas@gmail.com
Russian Federation, Saint-Petersburg

I. V. Piir

Institute of Chemistry FRC Komi SC UB RAS

Email: piyr-iv@chemi.komisc.ru
Russian Federation, Syktyvkar

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Supplementary files

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2. Fig. 1 Experimental and theoretical X-ray patterns and their difference profile for VEK and VEK-Ti0.1

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3. Fig. 2 Microphotographs of the VEC (composition according to EMF:(Mg0.19Mn0.19Ni0.18Co0.19Zn0.18)Nb2O6–δ) and VEC-Ti0.1 (composition according to EMF: 1 – (Mg0.18Mn0.19Ni0.18Co0.18Zn0.18)Nb1.9Ti0.10O6–δ, 2 –(Mg0.14Mn0.28Ni0.86Co0.56Zn1.20)Nb0.3TiO6–δ).

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4. Fig. 3. Dependences of the lattice parameter a (a) and the unit cell volume Vcell (b) on the ionic radius of cations in the A-positions of the columbite structure ANb2O6. The data on the lattice parameters and volume for individual columbites are taken from [22], the ionic radii are taken from Shannon [21].

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5. Fig. 4. Absorption spectra and Tauc dependences (insert) for VEC and VEC-Ti0.1 for a direct allowed electronic transition.

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6. Fig. 5. Nyquist plots for VEK and VEK-Ti0.1 at 200, 320, 460 and 600°C.

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7. Fig. 6. Frequency dependences of the imaginary component of the electrical modulus M'' and impedance –Z'' for VEK (a) and VEK-Ti0.1 (b), normalized graphs of the imaginary component of the electrical modulus M''/M''max on the normalized frequency f/fmax (c), dependence of the frequency at maximum M'' on the reciprocal temperature (d).

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8. Fig. 7. Frequency dependences of conductivity for VEC (a) and VEC-Ti0.1 (b) (the red line corresponds to the modeling of the curve according to Jonscher’s law), dependence of conductivity at direct current, obtained according to Jonscher’s equation, on the inverse temperature (c).

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9. Fig. 8. Conductivity dependences on the inverse temperature: (a) for VEC, VEC-Ti0.1 at direct current, for MgNb2O6 (1 kHz) [11] and MnNb2–xTixO6–δsub (x = 0, 0.1) [15] at alternating current; (b) for VEC and VEC-Ti0.1 when using silver electrodes (Ag|S|Ag) and an ion-blocking carbon electrode (Ag|S|C) (S-sample) at direct current.

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Note

2 Based on the materials of the report at the 17th International Meeting “Fundamental and applied problems of solid state ionics”, Chernogolovka, June 16–23, 2024.


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