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Proton and Oxygen-Ion Conductivity of the Pure and Lanthanide-Doped Hafnates with Pyrochlore Structure

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Abstract

In this work, a high-density ceramics Ln2Hf2O7 (Ln = La, Nd, Sm, Eu, Gd) were synthesized by mechanical activation followed by high-temperature synthesis at 1600°C (3–10 h) and their transport properties were compared with those of Ln2.1Hf1.9O6.95 (Ln = La, Nd, Sm, Eu) doped solid solutions. The total conductivity of ceramics was studied using impedance spectroscopy and dc four-probe method; for Ln2Hf2O7 (Ln = Sm, Eu), by determining the total conductivity as a function of oxygen partial pressure. The maximum oxygen-ion conductivity was observed for Gd2Hf2O7 (~1 × 10–3 S/cm at 700°C); it was shown to approach the conductivity of Gd2Zr2O7 (~2 × 10–3 S/cm at 700°C) for the first time. Thus, the gadolinium hafnate can be a promising material for further doping in order to obtain highly conductive electrolytes. Among pure rare-earth hafnates, the proton conductivity was reliably observed for Nd2Hf2O7 only; however, ac measurements detected low-temperature proton conductivity in the Gd2Hf2O7 up to 450°С as well. With a decrease in the lanthanide ionic radius, the oxygen-ion conductivity increased in the Ln2Hf2O7 (Ln = La, Nd, Sm, Gd) series. Although the conductivity of samarium hafnate is an order of magnitude lower than that of Gd2Hf2O7, it has a wide range of oxygen-ion conductivity (~10–18–1 atm at 700, 800°C); there is no contribution from hole conductivity in air, in contrast to Eu2Hf2O7. Among doped Ln2.1Hf1.9O6.95 pyrochlore solid solutions (Ln = La, Nd, Sm, Eu), the proton conductivity of ~8 × 10−5 S/cm at 700°C was shown in Ln2.1Hf1.9O6.95 (Ln = La, Nd). With a decrease in the lanthanide ionic radius, the proton conductivity disappeared; the oxygen-ion one, increased.

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Funding

This study was subsidized by the Ministry of Sciences and Higher Education of the Russian Federation in frames of the Semenov Federal Research Center for Chemical Physics State contract “Next-generation nanostructured systems with unique functional properties” (reg. no. 122040500071-0). The material conductivity study is performed in part in frames of the Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry contract (the State reg. no. АААА-А19-119061890019-5).

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Authors and Affiliations

  1. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow, Russia

    A. V. Shlyakhtina, I. V. Kolbanev & E. D. Baldin

  2. Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, Chernogolovka, Russia

    N. V. Lyskov

  3. National Research University “High Economy School”, Moscow, Russia

    N. V. Lyskov

  4. Institute of High Temperature Electrochemistry, Ural Branch, Russian Academy of Sciences, Yekaterinburg, Russia

    A. V. Kasyanova & D. A. Medvedev

  5. Ural Federal Yeltsin University, Yekaterinburg, Russia

    A. V. Kasyanova & D. A. Medvedev

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  1. A. V. Shlyakhtina
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Translated by Yu. Pleskov

Based on the materials of the 16th International Meeting “Fundamental Problems of Solid State Ionics,” Chernogolovka, June 27–July 7, 2022.

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Shlyakhtina, A.V., Lyskov, N.V., Kolbanev, I.V. et al. Proton and Oxygen-Ion Conductivity of the Pure and Lanthanide-Doped Hafnates with Pyrochlore Structure. Russ J Electrochem 59, 449–460 (2023). https://doi.org/10.1134/S1023193523060058

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